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RUBBER CHEMICALS
Introduction
Rubber processing chemicals are used extensively to impart performance and processability to rubber and the products made thereof. These chemicals are typically
organic compounds but several inorganic materials are also included under the
umbrella of rubber chemicals. The rubber compound is described as a mixture of
one or more rubber polymers (elastomers) with a combination of one or more of
llers, oils, and rubber chemicals (see RUBBER COMPOUNDING). The compound, once
vulcanized, provides technologically useful properties, such as may be applied to
tires, hoses, belts, tracks, and a variety of mechanical goods.
Vulcanization systems and antidegradants are the two dominant classes of
rubber chemicals, given that the largest class of rubbers used in industry (the socalled general-purpose rubbers) require cross-linking by sulfur or other curative
to provide meaningful performance, and require protection from oxygen and ozone
to provide meaningful service lifetimes (see ANTIOXIDANTS).
The present article reviews several recent developments in the eld of rubber
chemicals of particular interest to practitioners. These topics include
(1) non-nitrosamine curatives as a response to health concerns and legislation
(2) reversion-resistance curatives to enhance product durability and support
higher temperature cures
(3) silica-to-rubber coupling agents to support expanded use of silica ller
(4) nonstaining and persistent antidegradants for enhanced performance

Non-Nitrosamine Curatives
General-purpose rubbers are those made from the monomers isoprene, 1,4butadiene, and styrene. Each isoprene and butadiene unit contributes one
Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.

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carboncarbon double bond to the nal structure, plus a number of allylic hydrogen sites, which are the reactive centers for sulfur vulcanization. In sulfur
vulcanization, polymer chains are connected by covalent bonds (cross-linked) of
sulfur atoms or chains of sulfur atoms attached to the allylic positions of individual chains. The chemical components necessary for this process include the
polymer(s) with allylic hydrogens, elemental sulfur or a source of sulfur, plus
chemical promoters called accelerators and activators. In current practice, the
curative promoter package typically employs a primary accelerator, one or more
secondary accelerators, and zinc oxide and fatty acid (or a zinc fatty acid salt)
activator. Several excellent reviews have been written detailing the chemistry involved between these ingredients and the inuence they have on the development
of nal vulcanizate properties (19).
The benets of an optimized sulfur vulcanization system are several: economical, good kinetics, and good performance. Economical in that sulfur is very
inexpensive, and typical accelerators and activators are also low cost commodity chemicals. Good kinetics in that rapid cross-linking is achievable in a matter of a few minutes at usual curing temperatures of 130180 C but that the
rubber compound can withstand many minutes at processing temperatures often in the range of curing temperatures (ie, 100140 C) before the onset of
cross-linking.
The undesirable premature cross-linking of polymer chains in the processing
step is called scorch; the ability of the vulcanization system to withstand the heat of
processing without premature cross-linking is called scorch safety. This attribute
of delayed action (scorch safety) with fast cure is unique to accelerated sulfur
vulcanization, and allows for safe and rapid mixing and fabrication of rubber
compounds and parts coupled with rapid cure.
Good performance derives from the structure of the cross-links as a blend
of sulfur chain lengths, from one sulfur atom (monosuldic) to two (disuldic) to
three or more, up to eight and more (polysuldic). The differing chain lengths
impart differing physical characteristics: shorter chain impart heat stability and
resistance to permanent set, longer chain lengths impart tear resistance. The ratio
of sulfur to primary accelerator controls cross-link length distribution, and thus
can be used to tailor physical properties, even as the concentration of curatives
controls cross-link density, itself a dominant contributor to compound properties
such as modulus, strength, hardness, and abrasion resistance.
Figure 1 illustrates the curing process as measured by a rheometer. The
rheometer follows the development of cure state as a function of time. Vulcanization characteristics such as minimum torque M L (a measure of compound
green viscosity), onset of cure (T1 pt rise), M H (a measure of maximum cure state
reached), and T90% cure (time required to reach 90% cure state) are valuable
properties dening cure behavior. Likewise the rheometer cure prole can be broken into three regions of interest, an estimate of scorch safety, an idea of what
the cure state development looks like during the cross-linking phase, and how the
cross-linked vulcanizate network matures with additional heat.
Primary Accelerators. The primary accelerator of choice is a mercaptobenzothiazole sulfenamide of general chemical structure (1). Specic examples of
this class are listed in Tables 1 and 2.

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Fig. 1. Example of rheometer cure curve illustrating major cure attributes. To convert
dNm to in lb, multiply by 0.885.

The sulfenamide S N bond strength controls the scorch safety and cure rate.
The more labile this bond, the more readily the active cure promoter mercaptobenzothiazole is released at the onset of the cross-linking process. A family of
sulfenamides has been developed to span a range of cure rates. Common historical members of this class are shown in Table 3, arranged from fast curing to
Table 1. Nitrosamine-Generating Sulfenamides
Chemical name

Abbreviation

4-Morpholinyl-2-benzothiazole
disulde

MBSS

N-Oxydiethylene
benzothiazole-2-sulfenamide

MBS

N,N-Diisopropylbenzothiazole-2sulfenamide

DIBS

Chemical structure

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Table 2. Non-Nitrosamine-Generating Sulfenamides and Sulfenimides

Chemical name

Abbreviation

N-Cyclohexyl benzothiazole-2-sulfenamide

CBS

N-tert-Butyl-2-benzothiazole sulfenamide

TBBS

N-Dicyclohexyl-2-benzothiazole sulfenamide

DCBS

N-tert-Butyl-2-benzothiazole sulfenimide

TBSI

Chemical structure

slow, based on primary amines of weakening base strength (ie, a to b to c) and/or

increasing steric hindrance (ie, c to d to e) (10).
German legislation targeting elimination of stable and volatile nitrosamines
as by-products of vulcanization became effective in September 1988 as the Technical Rules for Hazardous Materials TRGS 552 (11,12). It recognized 11 nitrosamines as carcinogenic and set industry limits to exposure. Nitrosamines
are potent carcinogens in laboratory animal testing, and are suspect human carcinogens. The amines released from sulfenamide accelerators in the necessary
early step of vulcanization can combine with nitrogen oxides (NOx ) in the atmosphere to produce nitrosamines. Primary amines form unstable nitrosamines
that immediately decompose and do not constitute a health risk, whereas secondary amines produce stable nitrosamines by this process, (R)2 N N O). The
Table 3. Sulfenamide Structure Inuence or Cure Rate and Scorch Safety

a
CBS

TBBS

MBS

DIBS

DCBS

Cyclohexlyamine t-Butylamine
Base
Base strength
pK a 10.7
strength
pK a 10.5

Morpholine
Base
strength
pK a 8.3

Diisopropylamine Dicyclohexylamine
Base strength
Base strength
pK a 11.0
pK a 11.3
Steric hindrance
predominates

Steric hindrance
predominates

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Table 4. Comparison of sulfenamide cure properties

normalized to MBSa,b
Cure time (T90%)
Nitrosamine-generating
MBS
100
MBSS
27% shorter
DIBS
7% longer
Non-nitrosamine alternatives
CBS
27% shorter
TBBS
15% shorter
DCBS
31% longer

Scorch time
100
45% shorter
10% longer
29% shorter
22% shorter
30% longer

a Base compound: SBR, 50; polyisoprene, 50; N299 carbon black, 50;
naphthenic oil, 28; stearic acid, 1; ZnO, 3; antioxidant, 1; sulfur, 1.75;
sulfenamides at an equal molar level (4.74 mmol).
b Samples tested at 150 C.

immediate effect of the legislation was thus to target for elimination from vulcanization systems of all sulfenamides made from secondary amines able to form 1
of the 11 listed nitrosamines. The accelerators given in Table 1, MBS and MBSS
(derived from morpholine) and DIBS (derived from diisopropyl amine), had to be
replaced at least for European markets.
Compromise cure systems based on the faster and slower curing nonnitrosamine sulfenamides listed in Table 2 have been recommended as alternatives (1214). The sulfenimide variant N-tert-butyl-2-benzothiazole sulfenimide
(TBSI) was also produced to satisfy this need (15). As with DCBS the large steric
hindrance associated with the sulfenimide slowed the reaction kinetics, resulting
in slower cures and extended scorch safety.
Table 4 (16) makes a comparison of cure properties for the sulfenamides listed
in Tables 1 and 2 relative to MBS. No exact replacements are available for MBS,
MBSS, and DIBS, but DCBS can serve as an alternative for MBS and DIBS and
CBS and TBBS can serve as alternatives for MBSS. Proper adjustments in sulfur
and sulfenamide levels can provide similar cure performance. CBS and TBBS also
satisfy the need in providing rapid curing kinetics where required. Additional
scorch protection, if needed, can be obtained by application of the widely used
scorch inhibitor N-(cyclohexylthio)phthalimide (17).
Secondary Accelerators. Even bigger changes have come to the secondary curative segment. Three classes of chemicals served historically as secondary accelerators, useful in low levels to speed up sulfenamide cures: the thiuram (2) and dithiocarbamate (3) types, and the guanidine type (4). Specic examples for these classes are listed in Tables 5 and 6.

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Table 5. Nitrosamine-Generating Thiurams

Chemical name

Abbreviation

Tetramethylthiuram disulde

TMTD

Tetramethylthiuram monosulde

TMTM

Chemical structure

Two workhorse members of the thiuram class, particularly active in cure rate
as well as economical, are TMTD and TMTM (R= methyl, x = 2 and 1, respectively,
in 2). Both TMTD and TMTM are stable nitrosamine generators, as they liberate
the secondary amine, dimethyl amine, during vulcanization (12,13). Replacements
for these rubber chemicals has been a target of considerable technical effort in the
rubber industry. Several candidates have emerged, each with its own attributes.
None is a direct substitute for either TMTD or TMTM but several have proven
Table 6. Low or Non-Nitrosamine-Generating Thiurams, Dithiocarbamates, and
Guanidines
Chemical name

Abbreviation

N,N,N ,N Tetraisobutylthiuram
disulde

IBT

N,N,N
,N
Tetraisobutylthiuram
monosulde

IBM

Tetrabenzylthiuram
disulde

TBzTD

Zinc dibenzyldithiocarbamate

ZBEC

Diphenylguanidine

DPG

Di-o-tolylguanidine

DOPG

Chemical structure

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Table 7. Comparison of Cure Properties Relative to TMTDa of

Non-Nitrosamine Secondary Accelerator Alternativesb,c

TBzTD (eq molar, 0.67 phr)

IBT (eq molar, 0.47 phr)
ZBzDC (eq molar, 0.76 phr)

Cure time (T90%)

Scorch time

18% longer
18% longer
6% longer

33% longer
33% longer
Equal

a At

an equal molar level (0.30 phr).

compound: SBR, 50; Polyisoprene, 50; N299 carbon black, 50; naphthenic oil, 28; stearic acid, 1; ZnO, 3; antioxidant, 1; sulfur, 1.75; sulfenamides at an equal molar level (4.74 mmol).
c Samples tested at 150 C.
b Base

useful in non-nitrosamine cure packages. Cure properties of likely replacements

are compared to TMTD in Table 7 (16).
As secondary curatives, both TBzTD and IBT provide slightly longer cure
times but have the advantage of prolonging scorch safety. A much closer match
to TMTD is ZBzDC in both cure time and scorch time. When used at equal molar
concentrations, signicantly more weight of the non-nitrosamine replacements
are required versus TMTD.
TBzTD and ZBzTD do, in fact, generate stable nitrosamines from the secondary amine dibenzyl amine; however, this nitrosamine is nonvolatile and is
not readily released from the vulcanized product into the atmosphere. It is also
considered noncarcinogenic (18). Therefore, these materials are considered nonnitrosamine in usage. IBT likewise generates a stable nitrosamine but its level
has been claimed to be 100 times less than TMTD (19).
Sulfur Donors. A fourth class of sulfur vulcanization chemicals has been
affected by the move to non-nitrosamine generators: the sulfur donors. These are
organic chemicals which have a relatively high level by weight of sulfur atoms
that are able to be donated in the vulcanization process to create sulfur crosslinks. Elemental sulfur is the material of choice as a source of the sulfur atoms
which create these cross-links, but some articles cannot tolerate free sulfur for
requirements of color, solubility, or performance.
With regard to solubility, compounds which require a very high cure state
may require more sulfur than can be supplied as elemental sulfur. Sulfur has
a solubility limit of about 1 part per hundred rubber at room temperature (20)
and at higher levels will bloom, that is, crystallize out of solution onto the rubber compound surface, where it can be detrimental to processing, particularly to
tack, the ability of rubber to stick to itself or other rubber component in the
building of a composite product. So-called insoluble sulfur has been developed as
an alternative form of elemental sulfur: it has a polymerized long-chain structure
( Sx ) as opposed to crystalline sulfur (S8 rings) (21,22). Insoluble sulfur can be
substituted for crystalline sulfur and can be used at levels well above the solubility limits without bloom, in theory. In practice, however, insoluble sulfur will
revert to soluble sulfur at the temperatures often attained in mixing and shaping
rubber components, and thus can result in bloom in processing (23). Sufce it to
say that some alternative forms for sulfur are sometimes needed for processing.

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Table 8. Nitrosamine-Generating Sulfur Donors

Chemical name

Abbreviation

4,4 -Dithiodimorpholine

DTDM

4-Morpholinyl-2-benzothiazole
disulde

MBSS

N-OxydiethylenethiocarbamoylN
-oxydiethylenesulfenamide

OTOS

Tetramethylthiuram disulde

TMTD

Chemical structure

Likewise, for performance, sometimes a sulfur donor is needed as well. Elemental sulfur gives rise to variable cross-link lengths, regulated to some extent by
sulfur-to-accelerator ratio. In some applications, particularly those which require
very high temperature and or oxidative stability, one may need a preponderance of
cross-links of very low rank, mostly monosuldic. For this purpose, organic sulfur
donors may be useful (24).
Four conventional sulfur donor curatives employed historically are all nitrosamine generators, derived from either morpholine or dimethylamine, as shown
in Table 8. The industry has developed non-nitrosamine substitutes, as shown in
Table 9. As discussed earlier, TBzTD is used primarily as a secondary accelerator
to further accelerate cure while offering good scorch protection. Similarly, IBT
performs like TBzTD. CLD appears to be as active as DTDM in donating sulfur
evidenced by its ability to generate the same cure state as DTDM when used at
equal available sulfur levels. CLD however can introduce more scorch. These attributes are illustrated in Table 10 (16). TESPT has found value as a sulfur donor
in what has been described as an equilibrium cure, or EC for short (25). The concept relies on the slow release of sulfur from TESPT during the curing process
to control the reversion process illustrated in the rheometer chart of Figure 1.
Rhenocure SDT/S is a thiophosphite and thus not amine-based. It can be used
where high levels of short cross-links of the mono- and di-type are desirable for
long-term heat age stability (26). The Vultac class of Table 9 has found uses in
diene rubbers as partial or total replacement for sulfur (27). Benets claimed include improvements in aging properties and promoting covulcanization of blends.
Table 10 illustrates the sulfur-donating ability of the Vultac class by showing
Vultac 7 provides a similar cure state as sulfur when used as a total replacement.
One drawback is the introduction of scorch.
The rubber chemist has reacted vigorously to the challenge of eliminating volatile nitrosamine-generating chemicals in the workplace, even though
many had been xtures of the sulfur vulcanization process. Non-nitrosamine primary and secondary accelerators and sulfur donors are now available and used
extensively.

Table 9. Non-Nitrosamine Sulfur Donors

Chemical name

Abbreviation
TBzTD

N,N,N
,N
-Tetraisobutylthiuram disulde

IBT

Caprolactam disulde

CLD

Bis-(3-triethoxysilylpropyl)tetrasulfane

TESPT

Bis-(O,O-di-2-ethylhexyl-thiophosphoryl)polysulde

Rhenocure SDT/S

Alkylphenol disulde oligmer

Vultac

585

Tetrabenzylthiuram disulde

Chemical structure

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Table 10. Activity of Sulfur Donors Versus Free Sulfur Compared Using a
Rheometer Cure Tracea,b
Sulfur donor
Sulfur donor, phr
Available sulfur, phr
Delta Tq , dNm (cure state)
T90%, min
T1 pt rise, min

Sulfur

DTDM

CLD

Vultac 7

1.0
1.0
19.2
21.7
9.0

3.7
1.0
26.4
36.3
12.3

4.5
1.0
26.6
19.7
5.7

3.3
1.0
19.6
21.5
4.0

a Base compound: SBR, 50; polyisoprene, 50; N299 carbon black, 50; naphthenic oil, 28; stearic
acid, 1; ZnO, 3; antioxidant, 1; CBS, 1.25.
b Samples tested at 150 C.

Reversion-Resistance Curatives
Concomitant with the several benets of sulfur vulcanization described above
are certain deciencies owing to the complexity of the formation of, and instability of, the sulfur cross-link system. Reversion is dened as the anaerobic
(nonoxidative) degradation of sulfur-cured vulcanizates which results in a loss
of compound performance. This phenomenon is generally associated with loss in
cross-link density via thermal degradation of sulfur cross-links caused by heat
and/or extraneous accelerator fragments (28,29). It occurs during overcure conditions, elevated cure temperatures (30), and severe service conditions (31). Reversion is most pronounced for natural rubber, which tend to lose cross-links and
soften with heat and aging, whereas synthetics (polybutadiene, styrene-butadiene
copolymers (qv)) tend to add cross-links and harden with heat and aging (see
BUTADIENE POLYMERS).
Overcure, elevated cure temperatures, and severe service are all growing
trends industrially, particularly for large tires as are used in over-the-highway
trucks, off-the -road equipment, and aircraft tires, all of which also use a lot of
natural rubber. Manufacturing efciencies promote higher temperature cure conditions for better throughput. Tires are cured from heat applied at the outside
(mold) and inside (bladder) surfaces. For tires with thick rubber cross sections,
and given the poor thermal conductivity of rubber, a temperature gradient is produced from surfaces to interior. The surfaces may see signicantly more total heat
history than the interior. This may be so even allowing for slow cooling of the interior and continued cure of the inside after the tire is removed from the mold.
Cure systems are tailored for individual components to try to balance the cure
prole across the cross section, but a given thick tread may still be subjected to
a broad range of heat inputs, so that only a portion of that one component will
be optimally cured while a portion will be overcured. (No portion can be undercured without generating a useable product. Indeed, cure conditions are set so as
to require all portions of the tire to achieve a minimum acceptable level of cure.)
Tires, like other rubber goods, perform to ever higher levels: mileage, service life,
and service conditions. Still, high operating temperatures and loads may impart
reversion. Thus, there has been a growing interest in chemicals which inhibit the
tendency to reversion of sulfur-cured natural rubber.

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Fig. 2. Reversion during cross-link formation.

Reversion can occur during cross-link formation (high temperature cure) and
after cross-link formation (overcure or in service). These are shown pictorially in
Figures 2 and 3.
For processes which contribute to reversion seen during cross-link formation, several pathways can be envisioned contributing to loss in ultimate cure
state development. As Figure 4 shows, these pathways most likely involve desulfuration or decomposition of intermediate polythio-sulfurating species or the
polythio-benzothiazole cross-link precursor formed by the heat of the curing process. This decomposition pathway effectively reduces the concentration of active
cross-linking agents resulting in lower cross-link density. Also at very high temperatures as cross-links are forming, they may, in a similar manner, be immediately
desulfurated and decomposed.
In the development of maximum cure state, the initial cross-link structure,
which may be high in polysuldes, goes through a rearrangement process in which
the Zn-accelerator complexes, which promote curing, extrude sulfur from the initial cross-links and reutilize the extruded sulfur to form additional cross-links (29).
After the maximum cure state is established with a desired proportion of polysulde, disulde, and monosulde cross-links for compound performance, the network cross-link structures will continue to evolve with additional heat introduced

Fig. 3. Reversion after cross-link formation.

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Fig. 4. Reversion pathways during cross-link Formation.

during an overcure situation (30) or during the service life of the compound (31).
Figure 5 shows that this reversion process involves loss of polysulde cross-links
with the formation of more mono and disulde types and nally decomposition
of the mono and disuldic types yielding modications in the polymer backbone.
Modications would include carboncarbon double bond rearrangement, growth
of diene and triene structures, and isomerization of existing double bonds. For

Fig. 5. Cross-link network maturation and reversion with heat from curing or high temperature service.

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Fig. 6. Effect of temperature on cure rate and cure state. Base compound: NR, 100; N347
carbon black, 50; naphthenic oil, 8; stearic acid, 1; ZnO, 3; antioxidant, 0.75; sulfur, 3; TBBS,
0.75. To convert dNm to in lb, multiply by 0.885.

natural rubber, this results in creation of some trans double bonds in the otherwise all-cis structure. Additionally, unproductive (nonload bearing) cyclic suldes
increase in number in reversion: sulfur attached by both of its valences to neighboring segments of the same polymer chain. Zinc sulde is produced as a stable
but inactive by-product of both vulcanization and reversion. All these changes are
followed by a drop in cross-link density (3235).
The effect of cure temperature on the cure kinetics and cure state prole of a
simple carbon black lled, sulfenamide/sulfur cured natural rubber compound is
shown in Figure 6 (16). As shown in the growth of the cure state, an article which
would require 110 min to cure to its maximum cure state at 125 C can be cured
at 135 C in 50 min, at 150 C in 18 min, at 165 C in about 7 min, and at 182 C
in about 3 min. However, the maximum state of cure achieved keeps dropping as
cure temperature increases.
The same process continues beyond optimum or maximum cure state if cure
is allowed to continue (overcure). Again, as seen in Figure 6, the cure state now
drops from the maximum to attain a lower plateau. This decline is faster and more
pronounced as cure temperature increases. The window of time for near-optimum
cure narrows, and the regime of overcure grows.
Physical manifestations of reversion, beyond loss in cure state, include
(1)
(2)
(3)
(4)
(5)
(6)
(7)

loss in resilience
greater heat buildup
loss in abrasion resistanec
loss in wire adhesion
initial increase then large loss in tear and fatigue resistance
loss in modulus and hardness
loss in tensile strength

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How much of the decay in properties is due to cistrans isomerization, cyclic

suldes, growth of dienes, reduction in sulfur rank, and reduction in total crosslink density is a subject of ongoing research, but all processes likely contribute.
Because of the large demands put on rubber compounds to address issues of
increased productivity via high cure temperatures or increased service temperatures brought about by overloads and high speeds, reversion-resistance chemicals
are now becoming part of the compounders arsenal to combat reversion issues.
Reversion-resistance chemicals operate by one of two mechanisms:
(1) Relink polymer chains to maintain cross-link density. These may be via
sulfur or non-sulfur covalent bonding.
(2) Form heat stable cross-links that are more resistant to scission than conventional sulfur cross-links. These may or may not contain sulfur.
Several rubber chemicals have been developed to inhibit or compensate for
sulfur cross-link reversion. Several of these are shown in Table 11.
MPBM operates under the mechanism of forming heat-stable cross-links.
It has been reported that the network structures formed with MPBM are not
prone to revert (36,37) and offer heat resistance during high temperature curing
and overcure. Detailed mechanistic studies have found the major reactions occurring during vulcanization in sulfur-containing systems to be 1,2-cross-linking of
the imide double bond across polymer chains generating a heat-stable carbon
carbon cross-link. Additional reactions included homopolymerization, copolymerization giving multiple cross-links, and Michael addition reactions with 2mercaptobenzothiazole and amines derived from sulfenamide curatives as well as
other extraneous sulfur species formed during cure (38).
BCI-MX also provides its heat-resistant performance by the formation of
carboncarbon cross-links but does it by the mechanism of relinking polymer
chains to maintain cross-link density (38,39). The relinking mechanism takes
place only during reversion when sulfur cross-links are broken and in their place
cyclic suldes, dienes, and trienes are formed along the polymer backbone (16,35).
The structural differences of BCI-MX from MPBM prevent it from undergoing the
reactions discussed about MPBM. Instead, the citraconimide group undergoes a
DielsAlder addition reaction with these chain modications to relink polymer
chains and compensate for the lost, reverted, sulfur cross-links (3941). For BCIMX to be effective, some initial reversion must take place. This is nicely illustrated
in Figure 7 (16) which shows the reversion characteristics of BCI-MX versus the
same compound with no BCI-MX added.
As discussed earlier, TESPT functions as a reversion-resistant chemical by
the slow release of sulfur to compensate for cross-links lost (25). It has also been
found that TESPT leads to higher levels of monosuldic cross-links (42), which
yields improved reversion (thermal aging) resistance (43,44).
Both HTS and BDTCH can be classied as proceeding through the mechanism, which forms heat-stable cross-links that are more resistant to scission.
The cross-link has been referred to as a hybrid cross-link in which a hexylmethylene dithio group Sn [(CH2 )6 Sx ]k is the bridging group between two polymer chains (4549). In this scheme, k is presumed to be small. At high sulfur

Table 11. Anti-Reversion Agents

Chemical name

Abbreviation
MPBM

1,3-Bis(citraconimidomethyl) benzene

BCI-MX

Bis(3-triethoxysilylpropyl)tetrasulfane

TESPT

Hexamethylene bis-thiosulfate disodium salt dihydrate

HTS

Mixture of zinc salts of aliphatic and aromatic carboxylic acids

Activator 73

1,6-Bis(N,N-dibenzylthiocarbamyldithio)hexane

BDTCH

Trifunctional acrylate coagent

Sartomer SR534

591

N-N -m-phenylenedimaleimide

Chemical structure

R = aliphaticaromatic mix

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Fig. 7. Example of reversion-resistant agent effect on reversion (cure temperature 165 C).
Base compound: NR, 100; N347 carbon black, 50; naphthenic oil, 8; stearic acid, 1; ZnO, 3;
antioxidant, 0.75; sulfur, 3; TBBS, 0.75. To convert dNm to in lb, multiply by 0.885.

levels both n and x would be greater than 1. As reversion proceeds, the number
of n and x sulfur atoms would be reduced to one resulting in a hybrid cross-link
with monosulde linkages for thermal stability and the hexylmethylene bridge to
add exibility to the cross-link for improved tear and fatigue properties. Figure 7
illustrates the reversion-resistant capabilities the hybrid cross-link can offer.
Since Activator 73 A is a mixture of zinc salts of linear aliphatic and aromatic
carboxylic acids (50), it would be expected that the mechanism of action would be
similar to zinc stearate, which can extract sulfur from polysuldic cross-links and
reuse that sulfur to generate more cross-links (51). Ultimately this would result
in a network structure high in monosuldic content (42).
Trifunctional acrylates, such as Sartomer SR534, have been found to provide
reversion-resistant protection (52). Test results of the three trifunctional acrylate and methacrylate monomers, pentaerythritol triacrylate, trimethylolpropane
trimethacrylate, and trimethylolpropane triacrylate, versus BCI-MX prove interesting (53). Rheometer traces of cure development and reversion characteristics
with these trifunctional monomers duplicated BCI-MX behavior even to the point
of having initial reversion chemistry occurring before they became active. This
would suggest these materials operate by the same mechanism as BCI-MX.
To conclude this section, the rubber chemist has vigorously pursued materials and means to inhibit and counteract the tendency to reversion, so as to permit
higher temperature cures, buttress rubber goods against overcure, and permit
increasingly greater operating conditions and service lifetimes.

Silica-to-Rubber Coupling Agents

Rubber must be cross-linked to be technologically useful, hence the emphasis historically and in the two sections above, on chemicals to facilitate and optimize this
process. However, even cured rubber is practically of little value unless the rubber

Vol. 11

RUBBER CHEMICALS

593

is reinforced by a particulate ller (see FILLERS). Cured, unlled (gum) rubber

has very low tensile strength, and poor tear and abrasion resistance. Contrast a
pencil eraser or a rubber band to a tire tread or transmission belt, for example.
The early tires and rubber goods were lled with inert llers such as zinc oxide. The discovery about a century ago that carbon black (qv) greatly enhanced
rubber performance began the evolution of tough durable goods made from rubber. It turns out that very few other substances reinforce rubber as does carbon
black. None do at the same cost. Hence, even today, carbon black is the dominant
reinforcing ller for rubber, even as talc, calcium carbonate, kaolin clay, and other
lower cost, nonreinforcing llers retain uses in selected nontire applications.
The characteristics shared by reinforcing llers are few but vital:
(1) Small hard particles, with diameters upon ultimate dispersion below micron
size
(2) Ability of said particles to disperse in the rubber medium
(3) Ability of said particles to interact with themselves, so as to produce an
independent ller network, which interpenetrates with and synergistically
supports the polymer network. This attribute is called ller/ller interaction.
(4) Ability of said particles to interact with the polymer matrix. This attribute
is called polymer/ller interaction.

Carbon Black. Carbon black (qv) has all of these characteristics. Carbon
black is amorphous elemental carbon with a graphitic-like microcrystalline substructure (54). The furnace process rubber grades come in a range of particle and
aggregate sizes and shapes, with reinforcing grades in the 10100 nm ultimate
particle diameters. Carbon black disperses very well in general-purpose rubbers,
with which it shares an organic chemical nature. It has a strong self-afnity; once
a sufcient loading is achieved in a rubber matrix, it imparts electrical conductivity to the composite via the ller network, for example. This ller network is also
responsible for the enhanced low strain dynamic stiffness of lled rubber, and the
loss (recoverable upon relaxation) of this stiffness with strain. This phenomenon
is called the Payne effect (55). Finally, and most importantly, carbon black has a
strong afnity to general-purpose rubbers, as a function of attributes built into
the carbon black in its manufacture (surface activity) and the unsaturated organic structures of the polymers, such as carboncarbon double bonds, and styrene
units.
Much has been written on the nature of the carbon black/rubber interaction,
which is still not fully understood (selected references include References 5659).
One thing is clear: carbon black has a strong afnity to general-purpose rubbers. It
is manifest in the simple experiment called bound rubber or insoluble polymer
measurement. A sample of uncured rubber, which may or may not be devoid of
rubber chemical additives, is admixed with an amount of reinforcing carbon black.
The composite is then immersed in a solvent in which the polymer is soluble.
Whereas all, or all save any gelled portion, of the unlled rubber dissolves in the
solvent, the same polymer, as a carbon black lled composition, produces only a
portion of soluble polymer. For a typical recipe containing 3050 parts by weight

594

RUBBER CHEMICALS

Vol. 11

of carbon black per hundred parts rubber, a typical value for the nondissolved
or bound polymer might be 2040%. Empirically, the quantity of bound rubber
correlates with abrasion resistance, or tread wear for a (subsequently cured) tire
tread compound (60). Bound rubber cannot be measured on cured rubber, of course;
all but a fraction of a percent will be bound in that case, regardless of the type or
amount of ller. But the phenomenon of polymer/ller interaction, measured in
the uncured state, carries forward to the cured compound and product, in many
toughness and resilience related properties.
The search for alternative reinforcing llers to carbon black has continued
for decades, and has recently produced one material which offers in selected applications, even greater performance: precipitated silica.
Silica. Silica (a mineral with a repeat unit of SiO2 ) is, in its crystalline
form, as quartz and sand/sandstone, the most abundant compound on the earths
crust. Synthetic silica can be produced by a fumed process via silicon tetrachloride,
SiCl4 , or aqueous process, via sodium silicate, itself made from natural silica.
The product of the aqueous process is precipitated in an amorphous form, which
provides two of the attributes of a reinforcing ller: small particle size and high
degree of self-afnity or networking. The self-afnity is due to hydrogen bonding
between surface silanol groups (Si OH), which are present in large amount (57
per nm2 ) on the surface. Fumed silica has much fewer surface silanol groups. A
representation of the silica surface is given in Figure 8.
In the early 1990s, a new generation of precipitated silicas was developed:
the so-called highly dispersable silicas (HDS) (6165). This class provides another
vital attribute of a reinforcing ller for rubber: easy dispersability at high loadings
to submicron sizes.
The remaining attribute, polymer/ller interaction, is inherently missing
from silica but can be provided by the use of a specic class of rubber chemicals,
the silica-to-rubber coupling agents. Silica-to-rubber coupling agents have been
known since the 1960s, and had permitted limited use of silica ller, much of this
in nonblack mechanical goods and shoe soles. Use in tires was restricted to low
levels in skim compounds for wire adhesion and treads for cut resistance. A good
review of the state of the technology in the mid-1970s is given by Wagner (66).
With the advent of HDS, the ability to disperse silica to levels equal to that
of carbon black is now possible for the creation of highly silica-lled rubber compounds. Thus, there has been a revolution in growing use of silica in place of carbon black in tires since the early 1990s, requiring growing use of specic coupling
agents, whose number and chemistries have also expanded in this time period. A
description of this class of rubber chemicals follows.

Fig. 8. Silica surface chemistry.

Vol. 11

RUBBER CHEMICALS

595

The predominant chemical class of silica-to-rubber coupling agents are the

functionalized silane esters of general structure 5 (where typically R = Me, Et,
n = 3; R

= propylene [ (CH2 )3 ]; and X is a variable function). Many of these
were developed in the mid-1970s (67).

The most commonly used silane coupling agents (qv) for rubber are shown
in Table 12.
All Silane Coupling Agents (qv) work by a twofold bonding mechanism
(6870):
(1) The silane ester moiety hydrolyzes because of heat and moisture present
on the surface of the silica (RO Si HO Si) and the then-formed silanol
condenses with a silanol group on the silica surface to produce a siloxane
bond linking coupling agent to silica ( Si O Si ).
(2) The functional group (X above) on the other end of the coupling agent reacts
directly either with the polymer chain or with the vulcanization system so
as to provide a covalent bond between the coupling agent (already attached
to silica) and the polymer.
Step 1, reaction with silica, occurs in the mixing (with heat) of the silica,
rubber, and coupling agent. The polymer is as yet uncured and not bonded to
the ller. This step is called hydrophobation: the hydrophilic silanol containing
surface is converted to a hydrophobic organic modied surface. The silica loses
much of its self-afnity by this process, rendering it more compatible with rubber.
The Payne effect is reduced and may be nearly eliminated if hydrophobation is
thorough.
Step 2, reaction with polymer, occurs in the vulcanization step (with heat,
after curatives have been added in a lower temperature stage addition). Figure 9
shows the two-step coupling mechanism in the general case.
A subclass of silane rubber chemicals exists in which the X function of
structure 5 is replaced by an inert alkyl group, creating a silica-reactive but noncoupling process aid, of the general formula 6 (where R
= C1 C18 n-alkyl). These
materials can be very effective in reducing compound viscosity and the Payne
effect (71) but do not themselves provide cured compound reinforcement. A selected series of alkyl silanes is shown in Table 13. Alkyl silanes may be used
in conjunction with coupling agent silanes to balance processability and cured
performance.

The nature of function X is dependent on the nature of the cure system.

Historically, the methacrylate function was used for peroxide-cured rubber and
the mercapto function was rst used for sulfur-cured rubber (see a and b in
Table 12). Denitive studies of the role of coupling bonds on physical properties

Table 12. Selected Organofunctional Silane Coupling Agents for Silica-Filled Rubber
Chemical name
Chloro
3-Chloropropyltriethoxysilane

Formula

CAS no.

Flash
point, C

Supplier
(trade name)

[5089-70-3]

N/A

Degussa (Si
230)

Polychloroprene
Cl(CH2 )3 Si(OCH2 CH3 )3

Polyamide,
epoxy, acrylic

Amino
-Aminopropyltriethoxysilane

H2 N(CH2 )3 Si(OCH2 CH3 )3

[919-30-2]

96

-Aminopropyltrimethoxysilane

H2 N(CH2 )3 Si(OCH3 )3

[13822-56-5]

82

H2 N(CH2 )2 NH(CH2 )3 SiCH3 (OCH3 )3

[3069-29-2]

>93

N--(Aminoethyl)- aminopropylmethyldimethyoxysilane
Vinyl

GE Silicones
(A-1100)
Degussa (VP
Si 251)
GE Silicones
(A-1110)
GE Silicones
(A-2120)

596

Polyolen,
SBR, BR,
NR (peroxide
cure)

Vinyltriethoxysilane

CH2 =CHSi(OCH2 CH3 )3

[78-08-0]

44

Vinyltrimethoxysilane

CH2 =CHSi(OCH3 )3

[2768-02-7]

28

GE Silicones
(A-151)
Degussa (VP
Si 225)
GE Silicones
(A-171)
Acrylic, nitrile,
polyurethane,
SBR

Epoxy

-Glycidoxypropyltrimethoxysilane
Methacryloxy

Polymer
application(s)

CH2 CH(O)CH2 O(CH2 )3 Si(OCH3 )3

[2530-83-8]

110

GE Silicones
(A-187)
Butyl,
polyolen,
SBR, BR, NR
(peroxide)

 -Methacryloxypropyltrimethoxysilanea CH2 =C(CH3 )CO2 (CH2 )3 Si(OCH3 )3

[2530-85-0]

108

GE Silicones
(A-174)
Degussa (VP
Si 123)
Nitrile, SBR,
BR, NR
(sulfur cure)

Sulfur

-Mercaptopropyltrimethoxysilaneb

HS(CH3 )3 Si(OCH3 )3

[4420-74-0]

88

Bis-(triethoxysilylpropyl)tetrasuldec

[(CH3 CH2 O)3 Si(CH2 )3 ]2 S4

[40372-72-3]

104

Bis-(triethoxysilylpropyl)disulded

[(CH3 CH2 O)3 Si(CH2 )3 ]2 S2

[56706-10-6]

75

597

3-Octanoylthio-1-propyltriethoxysilanee CH3 (CH2 )6 (C=O)S(CH2 )3 Si(OCH2 CH3 )3 N/A

N/A

GE Silicones
(A-189)
Degussa (VP
Si 163)
GE Silicones
(A-1289)
Degussa (Si
69)
GE Silicones
(A-1589)
Degussa (Si
266, Si 75)
GE Silicones
(NXT)
SBR, BR, NR
(sulfur cure)

Thiocyanato
3-Thiocyanatopropyltriethoxysilane

N=C=S(CH2 )3 Si(OCH2 CH3 )3

[34708-08-2]

N/A

Degussa
(Si 264)
Polyurethane,
phenolic,
ureaformaldehyde

Miscellaneous

-Ureidopropyltrimethoxysilane

H2 N(C=O)NH(CH2 )3 Si(OCH3 )3

[23843-64-3]

99

-Isocyanatopropyltriethoxysilane

O=C=N(CH2 )3 Si(OCH2 CH3 )3

[24801-88-5]

77

a MAS.
b MPTMS.
c TESPT.
d TESPD.
e NXT.

GE Silicones
(A-1524)
GE Silicones
(A-1310)

598

RUBBER CHEMICALS

Vol. 11

Fig. 9. Silane coupling chemistry.

and tire performance of silica-lled tire rubber compounds was done by Wagner
using these two coupling agents (72).
Several other silanes were originally used to adhere rubber to glass substrates as well as applied to various rubbers with mineral llers such as clays.
Some of these are given in Table 12 as well.
Despite the performance benets of mercaptosilane, serious drawbacks limited its use in tires: a strong and bad odor, plus a large reduction in scorch safety,
resulting in inability to process the rubber. The mercapto group was simply too
reactive to the rubber, when combined with sulfur and curatives. Cross-linking
would initiate in mixing or extrusion.

Table 13. Selected Alkyl Silane (Silane Ester) Hydrophobating Agents for Silica-Filled
Rubber

Chemical name

Formula

CAS no.

Flash
point,

Supplier
(trade
name)
GE Silicones
(A-162)
Degussa (VP
Si 203)
GE Silicones
(A-137)
Degussa (VP
Si 208)
GE Silicones
(A-1630)
Degussa (VP
Si 216)

Methyltriethoxysilane

CH3 Si(OCH2 CH3 )3

[2031-67-6]

29

Propyltriethoxysilane

CH3 (CH2 )2 Si(OCH2 CH3 )3

[2550-02-9]

N/A

Octyltriethoxysilane

CH3 (CH2 )7 Si(OCH2 CH3 )3

[2943-75-1]

41

Methyltrimethoxysilane

CH3 Si(OCH3 )3

[1185-55-3]

12

Hexadecyltriethoxysilane CH3 (CH2 )15 Si(OCH2 CH3 )3 [16415-13-7]

N/A

Vol. 11

RUBBER CHEMICALS

599

In the 1970s, the rst step change improvement in coupling agents for sulfurcured rubber, as used in tires, came with the development of the tetrasulde silane,
TESPT (see c in Table 12) (67,68). Now, the mercaptan function was protected in
the form of a polysulde. To generate the active mercaptan, a sulfursulfur bond
cleavage was needed. By analogy to the generation with scorch safety of mercaptobenzothiazole (MBT) by the cleavage of the disulde MBTS, the tetrasulde silane
imparted scorch safety yet retained polymer reactivity of the mercaptosilane.
TESPT remained the industry standard coupling agent for sulfur cured rubber into the 1990s. With the development of HDS came expanded applications for
silica-based compounds, particularly in high performance passenger tire treads
which needed a combination of tread wear, low rolling resistance, and good wet
traction (73). This combination of performance attributes can be simultaneously
optimized to unique levels with silica. Recipes with 50100 phr silica were now
permissible and desirable.
As silica technology expanded to meet market performance targets, certain
processing deciencies grew in importance, and remedies through materials development emerged and continue to do so presently.
First, it became apparent that highly silica-lled compounds, even using
HDS, required longer mixing times and processed worse than their carbon black
counterparts (extrusion, tire building). It became clear that TESPT itself did not
have sufcient scorch safety for all operating conditions; the middle sulfursulfur
bonds in the polysulde bridge are relatively weak and can be broken, liberating
elemental sulfur to impart scorch. TESPT is a known sulfur donor curative, after
all. So, the market for TESPD expanded (see c and d in Table 12). The stronger
sulfursulfur bonds in TESPD provided extra processability in production while
retaining necessary polymer reactivity.
The newest sulfur silane coupling agent, NXT (see e in Table 12) (74,75) carries this approach even further. A substituted carbonyl group is used to protect
a mercaptosilane during processing and reaction at the silanol end with the silica (7), deprotection occurs during cure, catalyzed by curatives, to release active
mercaptan function (8), which, through reactions with the vulcanization system,
bonds to polymer (9), as shown below.

The rubber chemist has recognized and reacted to the growing trend to employ silica as reinforcing ller for rubber with development of multiple silane
ester coupling agents and alkyl silane process aids for improved processability
and performance.

600

RUBBER CHEMICALS

Vol. 11

Nonstaining and Persistent Antidegradants

General-purpose rubbers are susceptible to degradation by atmospheric oxygen
(O2 ) and ozone (O3 ).
Chemical antioxidants (qv) act to preserve rubber from degradation by
molecular oxygen. This degradation is manifest in hardening (cross-linking) for
polybutadiene and SBR and initial softening (chain scission) than hardening
for polyisoprene rubber (natural or synthetic). All rubbers lose tensile strength
and cut and tear resistance due to oxidation as well. Antioxidants inhibit the
free-radical autoxidation cyclic chain reaction process via several mechanistic
pathways. The primary antioxidants scavenge polymer carbon and hydroperoxy radicals by donation of an active hydrogen. Secondary antioxidants decompose hydroperoxides. A review is available, with attendant references to the
historical development of antidegradants and their mechanisms of action in rubber (76). Autoxidation and antioxidant mechanisms have also been reviewed
(77,78).
The hydrogen-bonded intermediate complex of a hindered phenolic antioxidant with a stable aminoxyl radical (TEMPO), used as a model for a hydrocarbon
oxidant, has been isolated and its structure determined, as conrmation of the
radical scavenging mechanism (79).
The principal classes of primary antioxidants for rubber remain the phenolics (nonblack articles) and amines (black-lled articles). Among the amine types
are the substituted diphenylamines, para-phenylenediamines (PPD, (10), where
R,R
= alkyl or aryl), and polymeric trimethyl-dihydroquinoline (TMQ). Representative phenolic antioxidants are given in Table 14, and selected amine antidegradants are given in Table 15. The majority of tire and mechanical goods
made from general-purpose rubbers are protected by the phenolic and amine antioxidants.

Macroscopically, ozonation leads to cracking of the rubber surface and ultimate product failure. A polar mechanism was proposed by Criegee for ozonation
of unsaturated hydrocarbon rubbers, with addition of ozone to the carboncarbon
double bond followed by decomposition of the intermediate ozonide leading to
cleavage of the polymer chain (80). Polymers without carbon bond unsaturation
in the backbone do not crack in the presence of ozone. Zhang recently proposed
a free-radical mechanism and attributed PPD antiozonant activity to its low ionization potential and ability to quench polymer radicals (81).
The PPD class of antidegradants provides by far the best antiozonant protection (for a review of antiozonants, see Reference 82). PPDs inhibit ozone degradation of rubber by multiple mechanisms (76,8385):
(1) Migration to the surface of the rubber article
(2) Competitive reaction with and scavenging of ozone at the surface

Table 14. Representative Phenolic Antioxidants Used in Rubber

Chemical name
a. Styrenated phenol

Structure

CAS no.
[61788-44-1]

b. Alkylated hindered phenol

Akcros Chemical (Akcrostab C53-P)

Flexsys (Montaclere SPH)
Great Lakes Chemical (Anox G2)
Goodyear Chemical (Wingstay S)
Harwick Standard (Antioxidant SP)
PMS Specialties (Prodox 120)
RT Vanderbilt (Wingstay S)
Sovereign Chemical (AO 47)
Sumitomo Chemical (Sumilizer S)
Crompton Uniroyal (Naugard SP)
Akrochem (Antioxidant 32, 33, 43)
CP Hall (Stabiwhite Powder 49-454)
Goodyear Chemical (Wingstay C, T)
Great Lakes Chemical (Anox T)
Inspec Fine Chemicals (Ionol K65, J65)
RT Vanderbilt (Wingstay C, T)

601
c. Polybutylated bisphenol A

Supplier (trade name)

[68610-51-5]

BF Goodrich (Goodrite Superlite)

RT Vanderbilt (Agerite Superlite)
Sumitomo Chemical (Sumilizer NW)

Table 14. (Continued)

Chemical name

Structure

CAS no.

Supplier (trade name)

602

d. 2,2 -Methylene-bis-(4methyl-6-t-butylphenol)

[119-47-1]

Akrochem (Antioxidant 235)

Ashland Chemical (Ashland AO 46)
Bayer Corp. (Vulkanox BKF)
CP Hall (Cyanox 2246)
Chemetall (Naftonox 2246)
Cytec Industries (Cyanox 2246)
Great Lakes Chemical (Lowinox 22M46)
Harwick Standard (Stangard PC)
PMC Specialties (CAO-5)
RT Vanderbilt (Vanox MBPC)
Raschig (Ralox 46)
Sumitomo Chemical (Sumilizer MDP-S)

e. Butylated reaction
product of p-cresol and
dicyclopentadiene

[68610-51-5]

Akrochem (Antioxidant 12)

Ashland Chemical (Ashland AO CL)
Goodyear Chemical (Wingstay L)
Great Lakes Chemical (Lowinox CPL)
PMC Specialties (Ralox LC LC)
Raschig (Ralox LC)
RT Vanderbilt (Wingstay L)
Sovereign Chemical (AOL 600)

f. Mixed methylenic bridged

adducts of alkylated
phenol and
dicyclopentadiene

Goodyear Chemical (Wingstay K)

RT Vanderbilt (Wingstay K)

603

g. Tetrakis methylene (3,5di-t-butyl-4-hydroxyhydro

[6683-19-8]

Akrochem (Antioxidant 1010)

Ashland Chemical (Ashland AO 610)
Akcros Chemicals (Lankromark LE373)
Ciba Specialty Chemicals (Irganox 1010)
Dover Chemical (Dovernox 10)
Great Lakes Chemical (Anox 20)
Mayzo, Inc. (BNX 1010)
PMC Specialties (Prodox 1010)
Raschig (Ralox 630)
Sumitomo Chemical (Sumilizer BP-101)

h. 1,3,5-Trimethyl-2,4,6-tris
(3,5-di-tert-butyl-4hydroxybenzyl)benzene

[1708-70-2]

Albemarle Corp. (Ethanox 330)

Ciba Specialty Chemicals (Irganox 1330)

Table 15. Representative Amine Antidegradants Used in Rubber

Chemical name
(abbreviation)

Structure

604

CAS no.

Supplier (trade name)

a. para-Styrenated
diphenylamine

[68442-68-2]

Akrochem (Antioxidant
POSDA)
Goodyear Chemical
(Wingstay 29)
RT Vanderbilt
(Wingstay 29)

b. Octylated
diphenylamine
(ODPA)

[68411-46-1]

Akrochem (Antioxidant
S)
BF Goodrich (Goodrite
Stalite S)
Bayer (Vulkanox
OCD/SG)
Crompton Uniroyal
(Octamine)
Flexsys (Permanox
ODPA)
Harwick Standard
(Stangard ODP)
RT Vanderbilt (Vanox
12)

26780-96-1

Ashland Chemical
(Ashland AO TQ-T)
Bayer (Vulkanox
HS/LG)
BF Goodrich (Goodrite
MA, Resin D)
Chemetall (Naftonox
TMQ)
Crompton Uniroyal
(Naugard Q)
Flexsys (Flectol TMQ)
Great Lakes Chemical
(Anox HB, HPG)
PMC Specialties (Ralox
TMQ)
RT Vanderbilt (Agerite
Resin D)
Raschig (Ralox TMQ)
Sovereign Chemical
(Pilnox TDQ)
Sumitomo Chemical
(Antigene RD-G)
Struktol (Struktol
TMQ)

d. Mixed diaryl-pphenylenediamine
(DPPD)

[68953-84-4]

Akrochem (Antiozonant
MPD-100)
Bayer (Vulkanox 3100)
Goodyear Chemical
(Wingstay 100, 200)
Crompton Uniroyal
(Novazone AS)
RT Vanderbilt
(Wingstay 100)

605

c. 2,2,4-Trimethyl1,2-dihydro
quinoline,
polymerized
(TMQ)

Table 15. (Continued)

Chemical name
(abbreviation)

Structure

CAS no.

Supplier (trade name)

606

e. N,N -Bis(1,4dimethylpentyl)-pphenylendiamine
(77PD)

[3081-14-9]

CP Hall (UOP 788)

Crompton Uniroyal
(Flexzone 4L)
Flexsys (Santoex
77PD)
UOP (UOP 788)

f. N-(1,3Dimethylbutyl)N
-phenyl-pphenylenediamine
(6-PPD)

[61931-82-6]
[793-24-8]

Akrochem (Antiozonant
PD-2)
CP Hall (UOP 588)
Chemetall (Naftonox
6PPD)
Crompton Uniroyal
(Flexzone 7L, 7P)
Duslo Sala (Dusantox
6PPD)
Bayer (Vulkanox 4020)
Flexsys (Santoex
6PPD)
RT Vanderbilt (Antozite
67P)
Sovereign Chemical
(Dusantox 6PPD)
Struktol (Struktol
6PPD)
Sumitomo Chemical
(Antigene 6C)
UOP (UOP 588)

607

g. Benzenamine,
N-[4-(1,3-dimethyl
(butyl)imino]-2,5cyclohexadien-1ylidene
(6-QDI)
h. 2,4,6-Tris(N-1,4dimethyl-pentyl-pphenylenediamino)1,3,5-triazine
(TAPDT)

[52870-46-9]

Flexsys (Q-Flex QDI)

Crompton Uniroyal
(Durazone 37)

608

RUBBER CHEMICALS

Vol. 11

(3) Formation, through its reaction products with ozone, of a protective lm at

the rubber surface
(4) Increase in the critical stress of the rubber article. The critical stress is the
applied static stress at which ozone cracking appears on the surface of a
rubber article exposed to ozone.
N-(1,3-dimethylbutyl)-N
-phenyl-p-phenylenediamine; abbreviated 6-PPD,
is a particularly versatile chemical offering a blend of antioxidant and antiozonant behavior combined with good rubber solubility and modest volatility, although other PPDs have applications as well. The diaryl PPDs have limited rubber solubility but lower volatility than 6-PPD. They provide excellent antioxidant
protection and decent persistence with diminished antiozonant protection.
All PPDs are highly staining and discoloring. This behavior is not necessarily
a problem in carbon black lled articles, but restricts usage in colored goodsor
even tires with colored components.
Two long-standing deciencies with the PPD antidegradants, lack of persistence and discoloration/staining, have been addressed, respectively, in recent
additions to the eld: 6-QDI, a dehydrogenated PPD, and TAPDT, a trimeric, high
MW form of PPD.
6-QDI (N-(1,3-dimethylbutyl)-N
-phenyl-p-quinonediimine, Table 15) offers
improved persistence because of its partial immobilization and binding to the
polymer matrix during mixing (86,87). As an efcient radical trap, 6-QDI acts as
a chemical peptizer to reduce natural rubber chain length and viscosity in mixing by capping cleaved polymer chain end radicals. 6-QDI still provides chemical
antidegradant protection similarly to its hydrogenated parent, 6-PPD, and is considered to be produced in situ from 6-PPD as part of the latters mechanism of
action in the cured rubber compound, as shown in equation 1 (88,89). 6-QDI is
also reported to preserve sulfur network rank stability better than 6-PPD and
impart improved abrasion resistance to a natural rubber tread compound relative
to PPD and TMQ antidegradants (90).

(1)
TAPDT
[2,4,6-tris-(N-1,4-dimethylpentyl-p-phenylenediamino)-1,3,5triazine, Table 15 provides reduced discoloration as a result of its increased
molecular size which imparts reduced mobility in the rubber matrix (91).
Discoloration results from bloom of ozonation by-products of the antidegradant
to the rubber surface. PPD containing compounds will stain adjacent compounds
in a composite structure because of migration of the PPD. An example is a black
sidewall protected by PPD staining the white sidewall of a tire. TAPDT does not

Vol. 11

RUBBER CHEMICALS

609

migrate like the monomeric PPDs. TAPDT gives excellent static ozone protection,
ex resistance, as well as antioxidant behavior, but does not provide the same
level of dynamic ozone protection (protection to product under stress, such as in
cyclic exing) as the monomeric PPDs (91). Blends of TAPDT and 6-PPD have
been shown to give excellent overall protection and durability (91).
A new partially graftable, aminic PPD of unspecied structure was recently
presented as another means to nonstaining antidegradant protection for rubber
(92).
In summary, the eld of rubber chemicals is both mature and ever evolving.
Recent advances and changes have been prompted by environmental concerns,
the move to higher efciency cures and processing, the pursuit of more durable
rubber products, and the growth of silica as a reinforcing ller.

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MARTIN P. COHEN
RICHARD M. DSIDOCKY
The Goodyear Tire & Rubber Company