RUBBER VULCANIZATES DEGRADATION

AND STABILIZATION

R. N. DATTA,* N. M. HUNTINK
TEIJIN TWARON BV, WESTERVOORTSEDIJK 73, 6800 TC ARNHEM, THE NETHERLANDS

S. DATTA, A. G. TALMA
AKZO NOBEL POLYMER CHEMICALS, ZUTPHENSEWEG 10, 7418 AJ DEVENTER, THE NETHERLANDS

ABSTRACT
Degradation of rubber vulcanizates in the presence and absence of air as well as in presence of ozone is reviewed
in this paper. The paper also outlines the means to overcome this undesirable phenomenon.
Under anaerobic aging conditions, which is termed as reversion, the vulcanizates are exposed to elevated tempera-
ture in the absence of oxygen. The consequence of this process is reflected in a decline in physical properties and per-
formance characteristics. These changes are directly related to modifications of the original crosslink structure.
Decomposition reactions tend to predominate and thus leading to a reduction in crosslink density and physical proper-
ties as observed during extended cure or when using higher curing temperatures. The decrease in network density is com-
mon when vulcanizates are subject to an anaerobic aging process. However, in the presence of oxygen, the network den-
sity is increased with the main chain modifications playing a vital role.
Over the years the rubber industry has developed several compounding approaches to address the changes in
crosslink structure during thermal aging. This paper gives a review of these compounding approaches. As with many for-
mulation changes in rubber compounding, there is a compromise that must be made when attempting to improve one per-
formance characteristic. For example, improving the thermal stability of vulcanized natural rubber compounds by reduc-
ing the sulfur content of the crosslink through the use of the more efficient vulcanization systems will reduce dynamic
performance properties such as fatigue resistance. The challenge is to define a way to improve thermal stability while
maintaining dynamic performance characteristics.
In the second part, the protection against aerobic ageing as well as in ozone environment is reviewed. The anti-
degradant effects are summarized and means to counteract are outlined. The most commonly used antidegradants are N-
isopropyl-N’-phenyl-p-phenylenediamine (IPPD) and N-(1,3-dimethylbutyl)-N’-phenyl-p-phenylenediamine (6PPD).
Although conventional antidegradants such as IPPD and 6PPD are still the most widely used antidegradants in rubber,
there is a trend and demand for longer-lasting and non-staining products. The relatively low molecular weight (MW)
antioxidants have undergone an evolutionary change towards higher molecular weight products with the objective to
achieve permanence in the rubber polymer, without loss of antioxidant activity. In the last two decades, several approach-
es have been evaluated in order to achieve this objective: attachment of hydrocarbon chains to conventional antioxidants
in order to increase the MW and compatibility with the rubber matrix; oligomeric or polymeric antioxidants; and poly-
mer bound or covulcanizable antioxidants. The disadvantage of polymer bound antioxidants was tackled by grafting
antioxidants onto low MW polysiloxanes, which are compatible with many polymers. New developments on antiozo-
nants have focused on non-staining and slow migrating products, which last longer in rubber compounds. Several new
types of non-staining antiozonants have been developed, but none of them appeared to be as efficient as the chemically
substituted p-phenylenediamines. The most prevalent approach to achieve non-staining ozone protection of rubber com-
pounds is to use an inherently ozone-resistant, saturated backbone polymer in blends with a diene rubber. The disadvan-
tage of this approach however, is the complicated mixing procedure needed to ensure that the required small polymer
domain size is obtained

CONTENTS

I. Part I: Protection Against Anaerobic Degradation of Rubber Vulcanizates . .437

A. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .437
B. Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .438
C. Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .438

*Corresponding author. Ph: +31 26 366 4396; Fax: +31 26 366 4110; email: [email protected]

436
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 437

1.Protection Against Reversion in Anaerobic Aging Environments . .438

2.Thiuram and Dithiocarbamate in Anaerobic Aging . . . . . . . . . .439
3.Dithiophosphate Accelerators . . . . . . . . . . . . . . . . . . . . . . . . . .440
4.Zinc Soap Activators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .442
5.Silane Coupling Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .443
6.Post Vulcanization Stabilizer, Disodium Hexamethylene
Bisthiosulphate (DHTS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .445
7. Antireversion Agent, 1,3-(bis citraconimidomethyl) Benzene,
Pekalink® 900 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .446
8. 1,6 –bis (N,N-dibenzylthiocarbamoyldithio)hexane,
BDTCH, Vulcuren KA 9188 . . . . . . . . . . . . . . . . . . . . . . . . . . .449
9. Miscellaneous Candidates . . . . . . . . . . . . . . . . . . . . . . . . . . . . .451
II. Part 2: Protection Against Aerobic Degradation and Ozone Environment .452
A. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .452
1. Oxidation and Anti-Oxidant Chemistry . . . . . . . . . . . . . . . . . . .453
2. Stabilization Mechanism of Antioxidants . . . . . . . . . . . . . . . . .455
3. Methods of Studying the Oxidation Resistance of Rubber . . . .457
4. Ozone and Anti-Ozonant Chemistry . . . . . . . . . . . . . . . . . . . . .458
5. Mechanism of Ozone Attack on Elastomers . . . . . . . . . . . . . . .459
6. Mechanism of Protection Against Flex Cracking . . . . . . . . . . .466
7. Trends Towards Long-Lasting Antidegradants . . . . . . . . . . . . .467
8. Protection Against Degradation in Oxidative Aging
Environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .473
9. Recent Developments with Sulfron 3000 . . . . . . . . . . . . . . . . . .476
III. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .477

I. PART I: PROTECTION AGAINST ANAEROBIC

DEGRADATION OF RUBBER VULCANIZATES
A. INTRODUCTION

Truck and off-the-road tires of today are frequently required to operate at high loads and
high speeds for extended periods of time. These severe operating conditions result in greater heat
build up than normally would be encountered under less demanding service conditions. As a con-
sequence, the excessive running temperature leads to reversion in compound components, which
may in turn lead to reduced tire durability or, in extreme circumstances, to tire failure.
Much effort was spent over the years to improve the reversion characteristics of tire com-
pounds. An established and, probably, best known approach is the use of so-called semi-efficient
cure systems comprising reduced sulfur levels and increased accelerator levels. However, though
effective in improving the vulcanizate’s resistance to reversion, this approach is only partially
successful since lowering of sulfur levels negatively influences other desirable properties such as
tear and flex/fatigue life.
With the advent of the radial tire, natural rubber (NR) usage has increased significantly. Its
tack and high green strength serve to maintain green tire uniformity during building and shaping
operations.
For both new and retreaded truck tires, however, the reversion characteristics of NR have
been considered to detract from wear performance, particularly in the early stages of tire life
where the tread surface has been subjected to the greatest degree of overcure. Accelerated wear
in later tire life may also occur due to thermal-oxidative degradation of the vulcanizate, particu-
larly cured with conventional cure systems. The need for chemicals that provide reversion resist-
438 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

ance is, therefore, of great interest.

This paper briefly reviews approaches to improve reversion resistance through the use of
antireversion chemicals, with emphasis on their applicability in truck tire tread compounds.
These antireversion chemicals are:
a) Thiuram or dithiocarbamates accelerators (Ia + Ib);
b) Dithiophosphate accelerators, Zinc o,o-dibutylphosphorothioate, ZBPD (II);
c) Zinc soap activators (Struktol A73) (III);
d) Silane coupling agent, Bis-(3-triethoxysilylpropyl)Tetrasulfide,TESPT (IV) Post vul-
canization stabilizer, Disodium hexamethylene thiosulphate DHTS (V) Antireversion
agent, 1, 3 bis-citraconimidomethyl benzene (Perkalink® 900) (VI) 1,6-bis (N,N-diben-
zylthiocarbamoyldithio) hexane, BDTCH, Vulcuren KA 9188 (VII);
h) Some other candidates.

Figure 1 illustrates the structural formula of these compounds.

FIG. 1. — Structures of Thiuram (Ia); Dithiocarbamate (Ib); Dithiophosphate (II);

Zinc soap activator (III); Silane coupling agent (IV); Post vulcanization stabilizer, HTS (V);
Antireversion agent, Perkalink 900 (VI); BDTCH, Vulcuren 9188 (VII).

B. EXPERIMENTAL
Compound formulations are shown in the respective data tables. Compound mixing was car-
ried out in a similar manner as described earlier.1
Stress strain and tear properties of the vulcanizates were measured using a Zwick Universal
Testing Machine (model 1445) in accordance with ISO 37 and ISO 34, respectively. Heat build
up was measured on a Goodrich Flexometer according to the method described in ASTM D623.
Fatigue to Failure properties were measured on a Monsanto Fatigue to Failure tester at 23 °C and
1.67Hz with 0-100% extension.
The volume fraction (Vr) in the swollen vulcanizate was determined by equilibrium swelling
in toluene using the method reported by Ellis and Welding.2 The Vr value so obtained was con-
verted to the Mooney-Rivlin elastic constant (C1) and finally to the concentration of chemical
crosslinks by using equations described in the literature.3,4 The proportions of mono, di, poly-
sulfidic and carbon-carbon crosslinks were determined using the method reported elsewhere.1

C. RESULTS AND DISCUSSION

1. Protection Against Reversion in Anaerobic Aging Environments. — A large number of
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 439

chemicals are available to address reversion concerns of compounds facing anaerobic ageing
conditions, such as overcure or exposure to heat under limited supply of air. The structures of
these chemicals are shown in Figure 1. Their functions with respect to performance characteris-
tics are described in this section.

2. Thiuram and Dithiocarbamate Accelerators. — Thiurams such as tetramethylthiuram

disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD) and dithiocarbamates such as zinc
dimethyldithiocarbamates (ZDMC) and zinc dibenzyldithiocarbamates (ZBEC) (Figure 1, 1a
and 1b, where M = Zn) give an improvement in reversion resistance when used together with
sulfenamide accelerators. This improvement is clearly demonstrated in Table 1.

TABLE I
EFFECT OF THIURAMS
Curatives, phr 01 02 03
Sulfur 2.3 2.3 2.3
CBS 0.6 0.6 0.6
TMTD 0 0.2 0
TBzTD 0 0 0.2
Mooney scorch, 121 °C, t5, min 30 18 27

Rheometer, 150 °C

ML, Nm 0.20 0.20 0.20

MH-ML, Nm 1.66 2.03 1.90
Ts2, min 3.8 2.5 3.4
T90, min 10.0 4.6 5.8

Reversion,a) % (150 °C/60’) 19.2 4.4 5.5

Formulations: NR,100; N-330, 50; aromatic oil, 3; zinc oxide, 5; stearic acid, 2; 6PPD, 2.
a) % Reversion = (R
max- Rmax+t)/(Rmax-min) x 100.

The restriction for the choice of TMTD, ZDMC and similar candidates is impaired due to
the N-Nitrosamine issue.5 In addition, although the combination of a sulfenamide and a thiu-
ram/dithiocarbamate (TMTD/ZDMC) shows improved reversion resistance, these systems suffer
from adverse effect on scorch and vulcanizate dynamic properties.6
Taking into consideration all aspects of compounding and industrial hygiene i.e. nitrosamine
problem, TBzTD or ZBEC are the better choice to target reversion resistance compounding with
thiurams or dithiocarbamates. Recently, Datta et al. reported7 that small amount (0.1-0.2phr) of
TBzTD is capable of improving reversion resistance without significantly affecting processing as
well as dynamic properties. The improvement in reversion resistance is due to the presence of a
high proportion of mono-sulfide crosslinks in sulfenamide/thiuram binary accelerator combina-
tions (Table II).
440 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

TABLE II
VULCANIZATES STRUCTURE – EFFECT OF THIURAMS, TMTD AND TBZTD
Mixes 01 02 03
Cure temp.,C 150 150 150
Cure time, min 10 4.6 5.8

Crosslink densitya)
Total 5.2 6.2 5.6
% Polysulfide 79.8 37.3 42.9
% Disulfide 16.9 8.8 10.7
% monosulfide 3.3 53.9 46.4
a) Crosslink densities expressed in gram mole/gram rubber x 105.

The improved reversion resistance of the sulfenamide/thiuram cure system is due to the for-
mation of zinc accelerator complexes, I and II, respectively, for TBzTD and TMTD (Figure 3).
The solubility of these complexes in rubber compounds determines the reactivity and conse-
quently desulfurization of initially formed polysulfidic crosslinks.7 This results in a network con-
taining a higher concentration of monosulfidic crosslinks.

FIG. 3. — Complex formed in sulfenamide-thiuram/zinc oxide acceleration.

3. Dithiophosphate Accelerators. — Dithiophosphates such as Zinc dibutyl dithiophosphate

(ZBPD, II, Figure 1) give an improvement in reversion resistance when used together with sulfe-
namide accelerators. This is clearly demonstrated by the cure data listed in Table III. The
improvement in reversion resistance is due to the greater proportion of mono and di sulfidic
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 441

crosslinks formed with the sulfenamide/ZBPD combination - Table IV .

TABLE III
VULCANIZATE CHARACTERISTICS
Curatives, phr 04 05
Sulfur 2.5 2.5
TBBS 0.6 0.2
ZBPD 0 0.75
Mooney scorch, 135 °C
T5, min 13.5 8.5

Rheometer, 144 °C
t2,min 8.7 5.7
t90,min 19.0 12.0
t90-t2,min 10.3 6.3
Reversion,a) % (160 °C/30’) 19.5 5.6
Formulations: NR,100; N-330, 50; naphthenic oil, 5; zinc oxide, 5; stearic acid, 2; 6PPD, 2.
a) % Reversion = (R
max- Rmax+t)/(Rmax-min) x 100.

TABLE IV
VULCANIZATE STRUCTURE – EFFECT OF DITHIOPHOSPHATE, ZBPD
04 05
Cure temp., °C 144 144
Cure time, min 20 13
Crosslink densitya)
Total 4.8 4.7
% Polysulfide 72 39
% Disulfide 10 17
% Monosulfide 18 44
a) Crosslink densities expressed in gram mole/gram rubber x 105.

Complex (I) (Figure 4), formed during sulfenamide/dithiophosphate curing reactions, is

responsible for the increased level of mono- and di- sulfidic crosslinks. It reacts with the initial-
ly formed polysulfidic crosslinks thereby reducing their sulfur rank.8

Complex (I)
FIG. 4. — Complex formed in sulfenamide-dithiophosphate acceleration.
442 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

The following advantages and disadvantages have been found for vulcanizates cured with a
sulfenamide/dithiophosphate combination.9
Advantages:
- Excellent reversion resistance;
- Improved cure rate;
- Reduced heat build up and dynamic set.
Disadvantages:
- Reduced scorch safety;
- Decline in initial fatigue properties;
- Decreased adhesion of rubber to brass coated steel.

4. Zinc Soap Activators. — These are mixtures of selected aliphatic and aromatic carboxylic
acids (III, Figure 1). Studies suggest that they are more soluble in a rubber matrix than the zinc
salt of stearic acid.10 Their mode of action is to react with initially formed polysulfidic crosslinks
thereby reducing their sulfur rank. The effect of a zinc salt activator on compound cure charac-
teristics, tensile properties and network structure is summarized in Tables V and VI.

TABLE V
CURE CHARACTERISTICS AND VULCANIZATE PROPERTIES
06 07
Struktol A 73, phr 0 3
Stearic acid, phr 2 0
Rheometer, 150 °C
Delta S, Nm 1.2 1.2
T2, min 8.3 7.7
T90,min
Cure rate,t90-t2, min
Reversion, % (150°C/2h)
Cure 150 °C/t90
Modulus100%, MPa 2.3 2.5
Modulus 300%, MPa 13.5 13.4
Tensile strength, MPa 30.2 31.0
Elongation at break, % 555 540
Fatigue to Failure, Kc 150 115
(0-100% extension)
Cure 150 °C/2h
Modulus100%, MPa 2.3 2.5
Modulus 300%, MPa 12.4 12.5
Tensile strength, MPa 23.1 23.9
Elongation at break, % 480 480
Formulations: NR, 100; N-375, 45; zinc oxide, 5; peptizer, 0.3; wax, 1.4; PVI, 0.5; 6PPD, 1.2; TMQ, 1.5; TBBS, 1.4;
sulfur, 1.4.
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 443

TABLE VI
VULCANIZATE STRUCTURE – EFFECT OF STRUKTOL A 73
06 07
Cure temp., °C 150 150
Cure time, min 13 13
Crosslink densitya)
Total 5.1 5.2
% Polysulfide 50 40
% Di sulfide 15 12
% Monosulfide 35 48
a) Crosslink densities expressed in gram mole/gram rubber x 105.

As shown in Table VI, the zinc salt activator produces a network containing a higher pro-
portion of monosulfidic crosslinks. The network degradation is accelerated by the presence of
additional complex as shown in Figure 5.

FIG. 5. — Complex formed from zinc salt activator.

However, while vulcanizate reversion resistance is improved, flex/fatigue characteristics is

hampered (Table V).

5. Silane Coupling Agent.— It has been reported11 that the silane coupling agent, Bis-(3-tri-
ethoxysilylpropyl)TetrasulfideTESPT (IV, Figure 1), in addition to its silica coupling role, is
capable of providing reversion resistance by acting as a sulfur donor, the so called equilibrium
cure concept.
The effect of the silane-coupling agent on cure characteristics, compound viscosity and vul-
canizate tensile properties are presented in Table VII. It is clear that TESPT decreases cure rate
(t90-t2) but improves processability through compound viscosity reduction. The increase in
modulus at the t90 cure condition can, in part, be attributed to the increase in crosslink density
(Table VIII), a result of its sulfur donor activity. The coupling agent also leads to a network con-
taining a higher proportion of monosulfidic crosslinks thereby providing improved reversion
resistance. The crosslink density data also indicate that TESPT is capable of maintaining a high-
er level of crosslink density on overcure compared to the control compound.
444 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

TABLE VII
CURE CHARACTERISTICS AND VULCANIZATE PROPERTIES
08 09
TESPT, phr 0 3
Rheometer, 150 °C
Delta S, Nm 1.55 1.85
ML, Nm 0.23 0.25
t2, min 2.5 1.7
t90, min 5.4 11.0
Cure rate, t90-t2, min 2.9 9.3
Mooney scorch, t5, 121 °C 16 10
Mooney viscosity, ML(1+4), 100 °C, MU 994 85
Reversion, % (150 °C/4h) 30 21
Cure: 150 °C/t90
Modulus100%, MPa 2.5 3.4
Modulus 300%, MPa 11.6 14.4
Tensile strength, MPa 27.0 26.8
Elongation at break, % 580 550
Cure: 150 °C/4h
Modulus100%, MPa 1.8 2.2
Modulus 300%, MPa 9.7 12.2
Tensile strength, MPa 22.5 24.7
Elongation at break, % 450 480
Formulations: NR, 100; N-220, 40; silica, 20; zinc oxide, 5; stearic acid, 2; aromatic oil, 3; resin coumaron, 3; wax, 1.0;
TMQ, 1.5; 6PPD, 2.5; CBS, 1.4; DPG,2; sulfur, 1.4.

TABLE VIII
VULCANIZATE STRUCTURE - EFFECT OF TESPT
Crosslink typea) Cure temp. 150 °C 08 09
Time
Total t90 4.90 5.34
60’ 3.86 5.01
4h 2.90 3.80
Polysulfide t90 2.45 2.35
60’ 1.16 1.80
4h 0.35 0.57
Disulfide t90 0.73 0.64
60’ 0.46 0.50
4h 0.23 0.38
Monosulfide t90 1.72 2.35
60’ 2.24 2.71
4h 2.32 2.85
a) Crosslink densities expressed in gram mole/gram rubber X 105.
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 445

6. Post Vulcanization Stabilizer, Disodium Hexamethylene Bisthiosulphate (DHTS). —

Hexamethylene bisthiosulphate disodium salt dihydrate (Figure 1, V) produces hybrid crosslinks
of the structure indicated in Figure 6. These hybrid crosslinks incorporate a flexible hexameth-
ylene group between the sulfur atoms attached to the polymer backbone. The sulfur/accelerator
levels and ratio, as in the normal sulfur vulcanization process will dictate the length of the sul-
fidic units.

FIG. 6. — Hybrid crosslinks formed by DHTS.

During overcure or during service, desulfurization of the polysulfidic crosslink structure

would occur as is normally observed during the reversion process. However, the structure of the
hybrid crosslink is such that desulfurization leads to a monosulfidic/hexamethylene crosslink
that retains the flexibility of a polysulfidic crosslink but possessing the thermal stability of a
monosulfidic crosslink – Figure 7.

FIG. 7. — Effect of reversion on final crosslink structure.

This built in flexibility provides compounds containing DHTS with good retention of
flex/fatigue properties.
The effect of DHTS in a typical NR stock is shown in Table IX. The data clearly show that
HTS improves reversion resistance and fatigue life before and following aging.
DHTS is also effective in maintaining adhesion to brass-coated steelcord.12
446 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

TABLE IX
IMPROVED REVERSION RESISTANCE WITH DHTS
Stocks 10 11
Sulfur 2.5 2.5
TBBS 0.6 0.6
DHTS 0.0 2.0
Rheometer reversion at 181 °C
% reversion in 60 min 35 23
Modulus reversion
Modulus 300%, Mpa
T90 at 144 °C 14.5 15.2
10 x t90 at 144 °C 11.3 14.8
t90 at 181 °C 10.1 13.3
Fatigue to Failure, Kc
(100% extension)
Unaged 189 251
Aged (2d/100 °C) 37 51
Heat build up, DT at 100 °C
T90 + 5’ at 144 °C 20 24
Blow out time, min at 100 °C
T90 + 5’ at 144 °C 17 17
Formulation: NR, 100; N-330, 50; zinc oxide, 5.0; stearic acid, 2.0; aromatic oil, 5.0; 6PPD, 2.0.

7. Antireversion Agent, 1,3 –(bis citraconimidomethyl) Benzene, Perkalink® 900. — The

antireversion agent 1,3-bis(citraconimidomethyl)benzene, Perkalink® 900, Figure 1 (VI), is
extremely effective at counteracting reversion. It reacts by a unique crosslink compensation
mechanism whereby sulfidic crosslinks, destroyed during the course of reversion, are replaced
by crosslinks based on the Perkalink® 900 molecule, Figure 8. In doing so the crosslink density
of vulcanizates can be maintained if overcure occurs during the vulcanization process or on aging
as encountered during tire service. As a result, mechanical properties are stabilized thereby
improving tire performance.

FIG. 8. — Mechanism of Perkalink® 900 reaction.

 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 447

The crosslink compensation mechanism occurs only at the onset of reversion as a result of
the formation of conjugated dienes and trienes along the polymer backbone.13 The antireversion
agent reacts with these conjugated structures via a Diels-Alder addition reaction.14 In doing so
Perkalink® 900 does not affect initial cure characteristics: scorch time, cure rate and t90.
Furthermore, it can be added to compounds with no additional change in formulation or modifi-
cation of mixing and processing conditions.
Heat generated in truck tires under demanding service conditions will lead to reversion of
compounds within the tire. The reversion is self-perpetuating since it lowers the modulus of the
compounds which in turn increases the rate of heat build up. Ultimately the integrity of the tire
suffers, resulting in reduced tire durability.
The incorporation of Perkalink® 900 in truck tread compounds will prevent reversion dur-
ing service thereby reducing the rate of heat build up. This will aid in maintaining the integrity
of the tire ensuring improved durability. Laboratory and tire test results are presented below
demonstrating the beneficial effect in an NR/BR based truck tire compound.
Compound formulations are shown in Table X. Pekalink® 900 was added at a level of 0.5
phr, as recommended for a semi-efficient cure system.

TABLE X
COMPOUND FORMULATIONS
Ingredients 12 13
(Control) (Pk900)
NR SMR CV 80 80
BR Buna CB 10 20 20
N-375 55 55
Zinc oxide 5 5
Stearic acid 2 2
Aromatic oil 8 8
6PPD 2 2
CBS 1.2 1.2
Sulfur 1.2 1.2
Perkalink® 900 - 0.5

The cure characteristics of both compounds are shown in Table XI.

TABLE XI
CURE CHARACTERISTICS AT 143 °C

12 13
(control) (Pk 900)
Rheometer MDR 2000 E
Torque max, Nm 1.72 1.70
Torque min, Nm 0.22 0.26
ts2, min 8.8 8.6
t90, min 14.6 14.8
Torque at 60 min, Nm 1.55 1.68
448 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

It is interesting to note that Perkalink® 900 does not affect initial cure characteristics.15 The
control compound shows a drop in torque on extended cure (60 minutes) despite the semi-effi-
cient cure system, whilst the test compound shows no drop in torque level, indicative of the anti-
reversion action provided by the Perkalink® 900.
The effect of Perkalink® 900 on vulcanizate physical properties cured at 143 °C, a typical
truck tire curing temperature, is shown in Table XII. Data are listed for optimum cure, t90, and
overcure, 60 minutes.

TABLE XII
PHYSICAL PROPERTIES OF VULCANIZATES CURED AT 143 °C FOR T90 AND 60 MINUTES
12 13
(control) (Pk 900)
Modulus 300%, Mpa, t90 12.1 12.2
60’ 10.9 12.0
Tensile strength, MPa, t90 27.4 27.5
60’ 25.4 26.4
Elongation at break, %, t90 575 580
60’ 560 530
Tear strength, kN/m, t90 109 107
60’ 98 93
Abrasion loss, DIN, mm3, t90 128 90
60’ 148 120
Fatigue to Failure, kC a) t90 145 150
60’ 70 100
a) 0-100% extension

The antireversion action provided by the Perkalink® 900 is demonstrated by the modulus
retention on overcure. Improved abrasion resistance, reduced abrasion loss, is also seen for the
compound containing the antireversion agent. Fatigue properties are not hampered
The most striking feature provided by Perkalink® 900 is the reduction in heat built up as
measured by the Goodrich Flexometer test, Figure 9.

FIG. 9. — Heat build up at 100 °C after 1 hour for samples cured at 2 x t90 and 60 minutes (BO – Blow Out).
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 449

Even at the extended cure of 60 minutes, the sample containing Perkalink® 900 did not show
any increase in heat build up compared to the sample cured for the shorter period of 2 x t90. The
control compound on the other hand experienced blow-out failure following a test time of 40
minutes. This significant reduction in heat build up provided by Perkalink® 900 should be reflect-
ed in improved truck tire performance.

8. 1,6 –bis (N,N-dibenzylthiocarbamoyldithio)hexane, BDTCH, Vulcuren KA 9188. -

BDTCH (Figure 1) is based on the dibenzylthiocarbamoyl leaving group with dithiohexane as a
crosslinker. Huls AG patented16,17 this substance in the early nineties. It was introduced18 to the
rubber industry as an effective antireversion agent. Based on structural similarity (Figure 10), a
comparison was made between BDTCH with TBzTD and with an additional amount of DHTS,
the moiety present in BDTCH.

FIG. 10. — Structures of TBzTD and BDTCH.

The compound formulation is presented in Table XIII.

TABLE XII
COMPOUND FORMULATION
Ingredients 14 15 16 17
(+TBzTD) (+BDTCH) (TBzTD+
DHTS)
NR SMR CV 100 100 100 100
N-330 50 50 50 50
Zinc oxide 5 5 5 5
Stearic acid 2 2 2 2
Aromatic oil 3 3 3 3
Santoflex 6PPD 2 2 2 2
Santocure CBS 1.5 1.5 1.5 1.5
Sulfur 1.5 1.5 1.5 1.5
Perkacit TBzTD - 0.2 - 0.2
Vulcuren, BDTCH - - 0.2 -
Duralink HTS - - - 0.1

The cure data of the mixes are shown in Table XIV.

450 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

TABLE XIV
CURE DATA OF THE MIXES AT 150 °C
Properties 14 15 16 17
(+TBzTD) (+BDTCH) (TBzTD+
DHTS)
Delta torque, Nm 1.81 1.90 1.94 1.92
Ts2, min 5.2 4.9 5.4 4.6
T90, min 9.1 6.7 7.2 7.4
Reversion, % (150 °C/1h) 9 3 2 2

It is interesting to note that both TBzTD and BDTCH behave similarly with respect to torque
development and cure time reduction. This is typical for any sulfenamide cure accelerated by thi-
urams or dithiocarbamates. The only difference observed between TBzTD and BDTCH is on the
scorch time. TBzTD is marginally worse than the mix containing BDTCH. This is expected
based on the chemistry of BDTCH. As shown in Figure 11, BDTCH cleaves to form TBzTD in
situ and this actually is the effective accelerator providing the boosting characteristics with no
effect on scorch data. The formation of TBzTD from BDTCH is shown in Figure 11.

FIG. 11.— Formation of TBzTD from BDTCH.

The formation of TBzTD from BDTCH suggests that the vulcanization chemistry of
BDTCH and TBzTD is similar, thus providing identical cure data as shown in Table XIV.
Addition of DHTS ( as it contains .S-(CH2)6-S.) is further explored (Mix 17). The cure data as
presented in Table XIV suggests that the mixes 17 and 16 behave similar except the scorch time
(ts2).
The effect of TBzTD and BDTCH on the vulcanizates physical properties at 150 °C is
shown in Table XV. Data are listed for optimum cure, t90, and overcure, 60 minutes.
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 451

TABLE XV
PHYSICAL PROPERTIES OF VULCANIZATES CURED AT 150 °C FOR T90 AND 60 MINUTES
Properties Cure State, min 14 15 16 17
Hardness, IRHD t90 70 72 72 72
60 68 72 72 72
Modulus, 300%, t90 15.2 16.0 16.2 16.3
Mpa 60 13.5 15.3 15.5 15.6
Tensile strength, t90 26.2 26.3 26.5 26.6
Mpa 60 25.0 25.8 25.6 25.9
Elongation at t90 520 500 490 500
break, % 60 510 490 480 490
Tear strength, t90 130 125 130 140
kN/m 60 95 110 110 120
Abrasion loss, t90 120 110 110 110
DIN, mm3 60 150 120 110 110
Fatigue to Failure a) t90 150 140 140 140
kC 60 90 110 110 120
a) Measured at constant energy.

The antireversion actions provided by TBzTD and BDTCH are demonstrated by modulus
retention on overcure. Better abrasion resistance, maintenance of tear and flex properties on
overcure are the consequences of heat stability offered by the network formed. The network den-
sity and the distribution of the crosslink types were measured and the data are tabulated in Table
XVI.

TABLE XVI
CROSSLINK DENSITY (CURE: 150 °C/T90)
Crosslink density a) 14 15 16 17
Total XL 5.50 5.71 5.73 5.75
Poly-S 2.39 2.30 2.22 2.20
Di-S 2.39 0.65 0.81 0.85
Mono-S 2.41 2.76 2.70 2.70
a) Crosslink density expressed in gram mole/gram RH X 105.

Comparing the crosslink density and distribution of crosslink types in different compounds,
it is clear that both TBzTD and BDTCH have similar network structure and hence the properties
are expected to be comparable. It can be therefore concluded that the functionality, -S-C( = S) -
N[(CH2)-Ph]2, plays the vital role and molecule derived from such a leaving group will provide
heat and reversion resistance features.

9. Miscellaneous Candidates. — Although the previously mentioned substances are com-

monly used materials in the rubber industry, but there are some other candidates cited in the lit-
erature to be effective antireversion agent. They are summarized in this section.
Multifunctional acrylates have been published19 to be effective antireversion agent. The
structures are shown in Figure 12.
452 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

FIG. 12. — Structures of acrylates.

Maleimides are reported20,21 to be effective crosslinkers in sulfur as well sulfur free vulcan-
ization. Recently, Vucht introduced22 2,2-dithiobis (phenylmaleimido) [FMI], Figure 13, and
claimed this as a chemical that increases the resistance against prevulcanization.

FIG. 13. — Structure of FMI.

The maleimides are good crosslinker but consumed during vulcanization and are not avail-
able during the reversion regime, i.e., during overcure or in service environments.23

II. PART 2: PROTECTION AGAINST AEROBIC

DEGRADATION AND OZONE ENVIRONMENT
A. INTRODUCTION

Rubber compounds can be degraded by reactions with oxygen, ozone, light, metal ions and
heat. Antidegradants protect rubber against aerobic aging (oxygen) and ozone attack. They are of
prime importance and play a vital role in rubber products to maintain the properties at service
conditions. Protection of rubbers or stabilization of crosslinked networks against anaerobic aging
can be achieved via other approaches: employing an EV-curing system, application of 1,3-
Bis(citraconimidomethyl)benzene, Hexamethylene-1,6-bis(thiosulphate) disodium salt dihy-
drate, Hexamethylene-1,6-bis(dibenzylthiuram disulfide), Zn-soaps, etc.24
Degradation by oxygen and ozone proceeds via different chemical mechanisms and results
in different effects on physical properties of rubber.25-36 Ozone degradation results in discol-
oration and eventual cracking of samples. Ozone degradation is primarily a surface phenomenon.
Oxygen degradation results in hardening or softening (depending on the base polymer) through-
out the rubber article. For example, vulcanizates that are based on natural rubber (NR), polyiso-
prene rubber (IR) and butyl rubber (IIR) preferably undergo cleavage reactions during the oxi-
dation process; they generally become softer. During progressive aging, a crosslinking mecha-
nism starts to dominate again: completely oxidized NR is usually hard and brittle. On the other
hand, vulcanizates obtained from styrene-butadiene-rubber (SBR), nitrile butadiene rubber
(NBR), chloroprene rubber (CR), ethylene propylene diene rubber (EPDM), etc. undergo
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 453

cyclization and crosslinking reactions that lead to hardening of the aged part. When completely
oxidized, these vulcanizates are turned into hard and brittle products. Rubbers that do not con-
tain C = C unsaturation, such as acrylic rubber (ACM), chlorinated polyethylene (CM), chloro-
sulfonated polyethylene (CSM), polychloromethyloxiran (CO), ethylene-ethyl acrylate copoly-
mer (EAM), epichlorohydrin rubber (ECO), ethylene propylene rubber (EPM), ethylene-viny-
lacetate copolymer (EVM), rubbers with fluoro and fluoralkyl or fluoralkoxy substituent groups
on the polymer chain (FKM), silicone rubber (Q), and others are much less sensitive to oxida-
tion than diene rubbers.
Although conventional antidegradants such as N-1,3-Dimethylbutyl)-N’-phenyl-p-
phenylenediamine (6PPD) and N-isopropyl-N’-phenyl-p-phenylenediamine (IPPD) provide pro-
tection against oxidation and ozonation, the protection lasts only short term. Longer-term pro-
tection requires a different class of antidegradants. Long-lasting antioxidants must be polymer
bound or must have a lower volatility and leachability than conventional antioxidants, whereas
long-lasting antiozonants must have a lower migration rate than the conventional antiozonants.
The purpose of this chapter is to review the developments on long term protection of rub-
bers against aerobic aging, especially on long-term (more than 5 years, depending on service
conditions) protection against ozone. Although numerous reviews of antioxidants and antiozo-
nants aspects have been published,25-36 in most cases they only cover one element (i.e. fracture
and fatigue in SBR and BR vulcanizates;28 the black sidewall surface discoloration and non-
staining technology;29 ozonolysis of natural rubber;34 etc. In this chapter attempts will made to
summarize most developments with emphasis on long-term antioxidant as well as antiozonant
protection.
1. Oxidation and Anti-Oxidant Chemistry: Introduction. — The changes in properties
observed on aging of different elastomers and their vulcanizates and of many other polymeric
materials, are well known. Antiozonants and antioxidants are employed to limit these changes.
However, the most effective antioxidant for one material may be ineffective, or even harmful in
another material or under different conditions. A rubber compounder must be aware of the effect
of oxygen attack on rubber and should know how to compound for oxygen resistance.

Mechanism of Rubber Oxidation. — The oxidation of polymers is most commonly depicted

in terms of the kinetic scheme developed by Bolland and coworkers.37 The scheme is summa-
rized in Figure 14. The key to the process is the initial formation of a free-radical species. At high
temperatures and at large shear forces, it is likely that free radical formation takes place by cleav-
age of carbon-carbon and carbon-hydrogen bonds.
Many elastomers are already observed to oxidize at moderate temperatures (below 60 °C),
where the energetics would not favor cleavage of carbon-carbon and carbon-hydrogen bonds.
Several studies have been conducted to determine whether trace impurities present in the poly-
mer systems could account for the relative ease of oxidation. Two separate studies concluded that
traces of peroxide were present in the polymer and that initiation occurred at low temperatures
due to the relatively easy homolysis of these peroxides into free radicals.38,39 Due to the high
reactivity of free radicals, only trace amounts of these peroxides need to be present to provide
initiation of the oxidative chain process. On the other hand, mechanical shear during processing
and bale compaction and localized heat during the drying and packaging of the raw polymer are
the most important causes of carbon-carbon and carbon-hydrogen bond cleavage. The resultant
free radicals react with oxygen to form the peroxides responsible for degradation.
The oxidation of hydrocarbon polymers resembles the oxidation of low molecular weight
hydrocarbons, with the polymer having its own internal source of peroxide initiators present. By
making the assumption that peroxides are present in even the most carefully prepared raw rub-
ber, the ease of oxidation of rubber at low to moderate temperatures can be understood.
454 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

Therefore, it is extremely important to compound rubber for extended oxidation resistance

through the use of protective additives and to be aware of pro-oxidant impurities present in the
rubber or the rubber compound.
Probably an important pro-oxidant for all rubbers is ultraviolet light. Blake and Bruce per-
formed a study of the oxygen absorption rates of unvulcanized NR rubbers under exposure to
UV-light.40 It was observed that exposure to light caused dramatic increases in the oxygen
absorption rate of NR. They studied the oxygen absorption rates of NR with various compound-
ing additives. A summary of their results is given in Table XVII. This table shows that phenyl-b-
naphtylamine, an additive previously used for prevention of rubber oxidation (hardly used any-
more because of toxicity reasons) can operate as a pro-oxidant under exposure to UV-light.
Fillers like zinc oxide, titanium dioxide, whiting and specially carbon black, lowered the rate of
oxygen absorption of NR with exposure to UV-light. This was attributed to the ability to make
the compound opaque, thus limiting the penetration of UV-light into the test films of NR. In the
case of benzidine and hydroquinone, the effects were attributed to the ability of these materials
to preferentially absorb the harmful UV-light. Thus, it is very important to consider the pro-oxi-
dant behavior of UV-light when compounding rubbers for extended life.

TABLE XVIII
OXIDATION OF NR PALE CREPE AT 46 °C, ACCELERATED BY UV-LIGHT17
Additive Absorption of O2
[cm3/h]
None 0.067
2% Sulphur 0.028
2% Benzidine 0.014
2% Hydroquinone 0.014
2% Phenyl-b-naphtylamine 0.076
5% Zinc oxide 0.010
1% P-33 Carbon black a) 0.018
a) P-33 is a fine thermal black, ASTM nomenclature N880.

The rate of peroxide decomposition and the resultant rate of oxidation is markedly increased
by the presence of ions of metals such as iron, copper, manganese and cobalt.36 This catalytic
decomposition is based on a redox mechanism, as in Figure 14b. Consequently, it is important to
control and limit the amounts of metal impurities in raw rubber. The influence of antioxidants
against these rubber poisons depends at least partially on a complex formation (chelation) of the
damaging ion. In favor of this theory is the fact that simple chelating agents that have no aging
protective activity, like ethylene diamine tetracetic acid (EDTA), act as copper protectors.
The rather simple sequence of reactions, as described in Figure 14a, is more complicated due
to other reactions when oxidizable impurities or compounding ingredients are present. There are
also the so called secondary processes, whereby peroxides and free radicals undergo reactions
leading to chain scission as well as crosslinking reactions. These reactions are closely related to
the primary oxidation process, so that for a given type of polymer or vulcanizate the degree of
deterioration of physical properties is generally proportional to the extent of oxidation.
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 455

FIG. 14a. — Bolland oxidation mechanism (RH=rubber hydrocarbon).37

FIG . 14b. — Decomposition of peroxides by ions of metals (Redox mechanism).

2. Stabilization Mechanism of Antioxidants. — Complete inhibition of oxidation is seldom

obtained in elastomers by addition of antioxidants or stabilizers. What is usually observed is an
extended period of retarded oxidation in the presence of the antioxidant. It has been demonstrat-
ed that during this period the rate of oxidation decreases with inhibitor concentration until the
optimum concentration is reached and then increases again. The rate of the retarded reaction is
affected by changes in oxygen concentration,41 in contrast to the uninhibited reaction, which pro-
ceeds at the same rate in oxygen or in air. These and other differences observed in the presence
of oxidation inhibitors reflect significant changes in initiation and propagation, as well as in ter-
mination reactions.
It is important to recognize that different types of inhibitors often function by different
mechanisms, and that a given antioxidant may react in more than one way. Thus a material that
acts as an antioxidant under one set of conditions may become a pro-oxidant in another situation.
The search for possible synergistic combinations of antioxidants can be conducted more logical-
ly and efficiently if we seek to combine the effects of different modes of action. Five general
modes of oxidation inhibition are commonly recognized:
1. Metal deactivators - Organic compounds capable of forming coordination complexes
with metals are known to be useful in inhibiting metal-activated oxidation. These com-
pounds have multiple coordination sites and are capable of forming cyclic structures,
which “cage” the pro-oxidant metal ions. EDTA and its various salts are examples of
this type of metal chelating compounds.
2. Light absorbers – These chemicals protect from photo-oxidation by absorbing the ultra-
violet light energy, which would otherwise initiate oxidation, either by decomposing a
peroxide or by sensitizing the oxidizable material to oxygen attack. The absorbed ener-
gy must be disposed of by processes which do not produce activated sites or free radi-
cals. Fillers which impart opacity to the compound (e.g. carbon black, zinc oxide) tend
456 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

to stabilize rubbers against UV catalyzed oxidation.

3. Peroxide decomposers – These function by reacting with the initiating peroxides to
form nonradical products. Presumably mercaptans, thiophenols, and other organic sul-
phur compounds function in this way.42 It has been suggested that zinc dialkyldithio-
carbamates function as peroxide decomposers (chain transfer agents), thus giving rub-
ber compounds good initial oxidative stability.
4. Free radical chain stoppers – These chemicals interact with chain propagating RO2• rad-
icals to form inactive products.
5. Inhibitor regenerators - These react with intermediates or products formed in the chain-
stopping reaction so as to regenerate the original inhibitor or form another product capa-
ble of functioning as an antioxidant.
Termination of propagating radicals during the oxidative chain reaction is believed to be the
dominant mechanism by which amine and phenolic antioxidants operate. The mechanism pro-
posed to account for this behavior is given in Figure 15 and Figure 16. The deactivation of R• via
chain braking electron acceptors (CBA) is demonstrated for a hindered amine light stabilizer
(HALS). The mechanism involves reaction of the HALS with a hydroperoxide, resulting in the
formation of a stable nitroxyl radical, that traps a hydrocarbon radical or abstracts a labile hydro-
gen from a hydrocarbon radical under formation of stable products. The hydroxylamine (CB-
AH) formed via this mechanism can be used for the stabilization of peroxide radicals.
An R• which is not fully deactivated via the mechanism described in Figure 15 reacts with
oxygen resulting in a peroxide radical. These peroxy radicals abstract a labile hydrogen from pri-
mary stabilizers like hindered phenols or secondary amines, resulting in less active hydroperox-
ides and preventing hydrogen abstraction from the polymer chain. The resulting antioxidant rad-
ical is more stable than the initial peroxy radical and terminates by reaction with another radical
in the system. This mechanism was proposed by Shelton,43 who demonstrated that replacement
of the reactive hydrogen in aromatic amine antioxidants by deuterium results in a slower abstrac-
tion of deuterium by peroxy radicals and therefore in a less effective antioxidant. It has also been
proposed that aromatic compounds such as phenols and aromatic amines can form p-electron
complexes with peroxy radicals, which terminate to form stable products.38 It appears that direct
hydrogen absorption, p-electron complex formation or both, describe the antioxidant action of
most amine and phenolic antioxidants. It is important that the level of antioxidant be kept at the
optimum, since excess antioxidant can result in a pro-oxidant effect (A-H + O2 → AOOH).
The mechanism of secondary stabilization by antioxidants is demonstrated in Figure 17.
Tris-nonylphenyl phosphites, derived from PCl3 and various alcohols, and thio-compounds are
active as a secondary stabilizer.44 They are used to decompose peroxides into non-free-radical
products, presumably by a polar mechanism. The secondary antioxidant is reacting with the
hydroperoxide resulting in an oxidized antioxidant and an alcohol. The thio-compounds can react
with two hydroperoxide molecules.
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 457

FIG. 15. — Deactivation of R• via chain braking electron acceptors (CB-A).

FIG. 16. — Primary stabilization via radical scavenging by hindered phenolics.

FIG. 17. — Secondary stabilization by phosphites and thio-compounds.

3. Methods of Studying the Oxidation Resistance of Rubber. — The most common test used
to study the oxidation resistance of rubber compounds involves the accelerated aging of tensile
dumbbell samples in an oxygen containing atmosphere. Brown, Forrest and Soulagnet recently
reviewed long-term and accelerated aging test procedures.45 The ASTM practices (D 454
(09.01); D 865 (09.01); D 2000 (09.01, 09.02); D3137 (09.01); D 572 (09.01); D 3676 (09.02);
D 380 (09.02)) for these tests clearly state that these are accelerated tests and should be used for
relative comparisons of various compounds and that these tests may not correlate to actual long-
term aging behavior. However, these tests are useful in evaluating aging-resistant compounds and
458 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

various antioxidant packages. The resistance of a compound to oxidation is generally measured

by the percentage change in the various physical properties (e.g. tensile strength, elongation at
break, hardness, modulus). For an elastomer which reacts with oxygen, resulting in crosslinking
(generally butadiene-based elastomers such as BR, SBR, NBR), the accelerated tests result in
increases in tensile modulus and hardness with a corresponding decrease in ultimate elongation.
For an elastomer which reacts with oxygen resulting in chain scission (generally isoprene-based
elastomers such as NR and IR), the accelerated aging tests result in decreases in tensile modulus
and hardness with either increasing or decreasing ultimate elongation, depending on the extent
of degradation.46 The most effective antioxidant package for a given elastomer compound gives
the smallest changes in physical properties during an accelerated aging test.
Thermoanalytical techniques such as DSC and TGA have also been widely used to study
rubber oxidation.47-50 The oxidative stability of rubbers and the effectiveness of various antioxi-
dants can be evaluated with DSC based on the heat change (oxidation exotherm) during oxida-
tion, the activation energy of oxidation, the isothermal induction time, the onset temperature of
oxidation, and the oxidation peak temperature.
Spectroscopic techniques like 13C-NMR,51 ESR,52 pyrolysis-GC/MS and pyrolysis-FTIR,53
X-ray diffraction54 and SEM55 techniques are also used to study rubber oxidation.

4. Ozone and Anti-Ozonant Chemistry: Introduction. — Layer and Lattimer30 and Bailey56
gave the historical background regarding protection of rubber against ozone.
As early as 1885 Thomson observed that stretched rubber cracked on aging.57 In the early
1920’s, a number of investigators studied this phenomenon in more detail. They found that cracks
occurred only in stretched rubber, formed in a direction perpendicular to the elongation, and grew
most rapidly at an elongation of about 10%.58,59 Fabry and Buisson observed crack formation in
the presence of ozone, but questioned the influence of this ozone. Ozone was believed to be pres-
ent only in the upper atmosphere and not at those places where rubber is commonly used.60 By
1935, analytical techniques had developed sufficiently to be able to measure that trace amounts
of ozone, parts per hundred million (pphm), were present in the troposphere.61 Even so, these
trace amounts were felt to be too insignificant to be the cause of severe damage. Therefore, other
factors responsible for cracking were sought. Sunlight seemed to be an indispensable factor;
hence names like “suncracking” and “sunchecking” were frequently used to describe this phe-
nomenon. Direct sunlight, however, was not necessary, since cracking occurred equally well on
the shady side as well as on the sunny side of the rubber.62 Also dust was thought to be respon-
sible for cracking. Dust, once settled on the rubber and activated by sunlight, would give off oxi-
dizing moieties and crack the rubber.62,63 Today, we know that only a few pphm of ozone in our
atmosphere can cause severe cracking of rubber and that sunlight is responsible for its formation.
Ozone in the atmosphere is formed by the chemical reaction of atomic and molecular oxy-
gen:

O + O2 → O3

At high altitudes, the oxygen atoms are generated by the photolysis of molecular oxygen by
the far ultraviolet light of the sun. In the troposphere, where only longer wavelength ultraviolet
light exists, photolysis of nitrogen dioxide is the major source of oxygen atoms:64

NO2 + hv → NO + O

The nitric oxide produced in this reaction reacts with ozone to regenerate oxygen and nitro-
gen dioxide:
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 459

NO + O3 → NO2 + O2

An equilibrium is established which gives rise to a so-called photostationary-state relation,

which depends on the relative rates of the above reactions:

[O3] = j[NO2] / k[NO]

where j = reaction rate of the formation of O3; k = reaction rate of the decomposition of O3.
Based solely on this relationship, it has been predicted that the ozone concentration should
be about 2 pphm at solar noon in the U.S. Indeed,30 in unpolluted environments, ozone concen-
trations usually are in the range of 2 to 5 pphm. However, in polluted urban areas, ozone con-
centrations can be as high as 50 pphm. Peroxy radicals formed from hydrocarbon emissions
cause this enhanced ozone concentration. These radicals oxidize nitric oxide to nitrogen dioxide,
thereby shifting the above steady state relationship to higher ozone levels.
Since ozone is generated by photolytic reactions, anything which affects available sunlight
will affect the ozone concentration. Consequently, ozone levels are the highest in the summer
months, when the days are longer and the sun is more intense.65 Similarly, ozone levels are high-
est near midday and decrease almost to zero at night.66 Temperature has little effect on ozone for-
mation.
The ozone-cracking problem was first taken seriously by the United States Government in
the early 1950’s. On reactivating military vehicles, moth-balled since World War II, it was found
that tires were severely cracked and useless. Government-sponsored research projects rapidly led
to the discovery of p-phenylenediamine antiozonants. Since then, these original antiozonants
have been displaced by longer lasting p-phenylenediamine derivatives.

5. Mechanism of Ozone Attack on Elastomers. — Ozone cracking is an electrophilic reaction

and starts with the attack of ozone at a location where the electron density is high.67 In this
respect unsaturated organic compounds are highly reactive towards ozone. The reaction of ozone
is a bimolecular reaction where one molecule of ozone reacts with one double bond of the rub-
ber, as can be seen in Figure 18. The first step is a direct 1,3-dipolar addition of the ozone to the
double bond to form a primary ozonide (I), or molozinide, which is only detectable at very low
temperatures. At room temperature, these primary ozonides cleave as soon as they are formed to
give an aldehyde or ketone and a zwitterion (carbonyl oxide). Cleavage occurs in the direction,
which favors the formation of the most stable zwitterion (II). Thus, electron donating groups,
such as the methyl group in natural rubber, are predominately attached to the zwitterion, while
electron-withdrawing groups, such as the chlorine in chloroprene rubber, are found on the alde-
hyde.68 Normally, in solution, the aldehyde and zwitterion fragments recombine to form an sec-
ondary ozonide, but higher molecular weight polymeric peroxides (III) can also be formed by
combination of zwitterions. The presence of water increases the rate of chain cleavage, which is
probably related to the formation of hydroperoxides. The same chemistry occurs on ozonation of
rubber, in solution and in the solid state.69
460 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

FIG. 18. — Ozone attack on double bonds.

Due to the retractive forces in stretched rubber, the aldehyde and zwitterion fragments are
separated at the molecular-relaxation rate. Therefore, the ozonides and peroxides form at sites
remote from the initial cleavage, and underlying rubber chains are exposed to ozone. These
unstable ozonides and polymeric peroxides cleave to a variety of oxygenated products, such as
acids, esters, ketones, and aldehydes, and also expose new rubber chains to the effects of ozone.
The net result is that when rubber chains are cleaved, they retract in the direction of the stress
and expose underlying unsaturation. Continuation of this process results in the formation of the
characteristic ozone cracks. It should be noted that in the case of butadiene rubbers a small
amount of crosslinking occurs during ozonation. This is considered to be due to the reaction
between the biradical of the carbonyl oxide and the double bonds of the butadiene rubber.70
The reaction of ozone with olefinic compounds is very rapid. Substituents on the double
bond, which donate electrons, increase the rate of reaction, while electron-withdrawing sub-
stituents slow the reaction down. Thus the rate of reaction with ozone decreases as follows: poly-
isoprene > polybutadiene > polychloroprene.71 The effect of substituents on the double bond is
clearly demonstrated in Tables XIX and XX. Rubbers that contain only pendant double bonds
such as EPDM, do not cleave since the double bond is not in the polymer backbone.
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 461

TABLE XIX
RELATIVE SECOND ORDER RATE CONSTANTS FOR OZONATIONS OF SELECTED OLEFINS IN CCl4 AT ROOM TEMPERATURE67
Olefins Reaction rate
Krel [l/mole.s-1]
Cl2C = CCl2 1.0
ClH = CCl2 3.6
H2C = CCl2 22.1
cis-ClCH = CHCl 35.7
trans-ClCH = CHCl 591
H2C = CHCl 1180
H2C = CH2 25000
H2C = CHPr 81000
H2C = CMe2 97000
cis-MeCH = CHMe 163000
Me2C = CHMe 167000
Me2C = CMe2 200000
1,3-Butadiene 74000
Styrene 103000

TABLE XX
RELATIVE SECOND ORDER RATE CONSTANTS FOR OZONATIONS OF
UNSATURATED RUBBERS IN CCl4 AT ROOM TEMPERATURE30,56,71
Rubbers Reaction rate
Krel [l/mole.s-1]
CR 1.0
BR 1.5
SBR 1.5
IR 3.5

Although the cracking of rubbers is related to the reaction of ozone on the double bond, it
must be mentioned that ozone reacts also with sulphur crosslinks. These reactions however are
much slower. The reaction of ozone with di- and polysulfides is at least 50 times slower than the
corresponding reaction with olefins.72

RSSSR + O3 → SO2 + RSO2-O-SO2R (+ H2O)→ 2 RSO2H

Unstretched rubber reacts with ozone until all of the surface double bonds are consumed,
and then the reaction stops.73 The reaction is fast in the beginning, the rate progressively decreas-
es while the available unsaturation is depleted and ultimately the reaction stops. During this reac-
tion, a gray film, or frosting, forms on the surface of the rubber, but no cracks are noticed. The
thickness of this film of ozonized rubber is estimated to be 10 to 40 molecular layers (60 to 240
A°) thick, based on the measurements of the ozone absorbed by unstretched rubber74,75
Disrupting this film by stretching brings new unsaturation to the surface and allows more ozone
to be absorbed.
462 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

Cracks are only observed when the rubber is stretched above a critical elongation. Two fac-
tors determine cracking under static conditions: the critical stress necessary for cracks to form
and the rate of crack growth. It was established that all rubbers require the same critical stored
energy for cracking to occur.76 This energy is thought to be the energy necessary to separate the
two surfaces of a growing crack. Thus depending on the stiffness of the polymer, cracks are
formed above a certain elongation. Cracks will only form and grow if the ozonized surface prod-
ucts are moved aside to expose underlying unsaturation. Energy of some form is required to
accomplish this. Under static conditions, this is equal to the critical stored energy. Under dynam-
ic conditions, flexing by itself supplies the energy to disturb the surface and no critical energy is
required.
The rate of crack growth depends on the polymer and is directly proportional to the ozone
concentration. The rate of crack growth is independent of the applied stress as long as it exceeds
the critical value. The rate of crack growth also depends on the mobility of the underlying chain
segments of rubber, which is necessary to untangle and position double bonds for further attack
by ozone. Consequently, anything that will increase the mobility of the rubber chains will
increase the rate of crack growth. For example, the slow crack growth rate in IIR becomes equal
to that of NR and SBR when sufficient plasticizer is added or when the temperature is raised.77
Conversely, decreasing chain mobility diminishes the crack growth rate. For this reason, increas-
ing the crosslinking density in some cases decreases mobility and reduces the rate of crack
growth.

Mechanism of Anti-Ozonants. — Rubbers can be protected against ozone by use of chemi-

cal antiozonants and via several physical methods. The chemical antiozonants protect rubber
under both static and dynamic conditions, whereas the physical methods are more related
towards protection under static conditions.

Protection Against Ozone Under Static Conditions. — There are several physical methods
that can be used to protect rubber against ozone. They are wrapping, covering, or coating the rub-
ber surface.78. This can be accomplished by adding waxes to the rubber and/or adding an ozone
resistant polymer which increases the critical stress. Waxes are the most important in this respect.
Two types of waxes are used to protect rubber against ozone, paraffinic and microcrystalline.
Paraffinic waxes are predominantly straight chain hydrocarbons of relatively low molecular
weight of about 350 to 420. They are highly crystalline due to their linear structure and form
large crystals having a melting range from 38 to 74 °C. Microcrystalline waxes are obtained from
higher molecular petroleum residuals and have higher molecular weights than the paraffinic
waxes, ranging from 490 to 800. In contrast to the paraffinic waxes, microcrystalline waxes are
predominantly branched, and therefore form smaller, more irregular crystals which melt from
about 57 to 100 °C. Waxes exert their protection by blooming to the surface to form a film of
hydrocarbons which is impermeable to ozone. Protection is only obtained when the film is thick
enough to provide a barrier to the ozone. Thus the thicker the film, the better the protection. The
obtained thickness of the bloom layer depends both on the solubility and the diffusion rate of the
wax, which depend on the temperature. Bloom occurs whenever the solubility of the wax in the
rubber is exceeded. Therefore, at temperatures lower than 40 °C, the smaller and more soluble
paraffinic waxes provide the best protection. Lowering the temperature reduces the solubility of
the paraffinic waxes and increases the thickness of their bloom. Yet, their small size allows them
to migrate rapidly to the surface, in spite of lower temperatures. Conversely, as the temperature
increases, the high solubility of the paraffinic waxes becomes a disadvantage. They become too
soluble in the rubber and do not form a thick enough protective bloom. Microcrystalline waxes
perform better at higher temperatures, since higher temperatures increase their rate of migration
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 463

to the surface and this allows more wax to be incorporated into the rubber. Therefore, blends of
paraffinic and microcrystalline waxes are commonly used to guarantee protection over the widest
possible temperature range.79 Combinations of waxes and chemical antiozonants show synergis-
tic improvement in ozone resistance.80 Presence of the antiozonant results in a thicker bloom
layer.
Another way to protect rubber against ozone is to add an ozone-resistant polymer (i.e. EPM,
EPDM, halobutyl, polyethylene, polyvinyl acetate, etc.) to the rubber. Microscopic studies of
these mixtures show that the added polymer exists as a separate, dispersed phase.81
Consequently, as a crack grows in the rubber, it encounters a domain of the added polymer,
which reduces the stress at the crack tip. This raises the critical stress required for cracking to
occur, and crack growth ceases. Under dynamic conditions, where almost no critical stress is
required, these polymer blends do not completely prevent cracking. In this case they function by
reducing the segmental mobility of the rubber chains and this slows the rate of crack growth. This
method is effective when the polymer is added at a level between 20 and 50%. Higher levels do
not result in further improvement of the ozone resistance.82 At lower levels, propagation cracks
circumvent the stress-relieving domains or will not reduce segmental mobility sufficiently. This
method of protecting rubber against ozone is used on a limited basis, since vulcanizates of these
blended rubbers frequently exhibit poorer properties. However, till today it is the only effective
nondiscoloring method of protecting rubber under dynamic conditions.

Protection Against Ozone Under Dynamic Conditions. — Under dynamic conditions, i.e.
under cyclic deformations (stretching and compression) the physical methods to protect against
ozone are no longer valid. Chemical antiozonants have been developed to protect rubber against
ozone under such dynamic conditions. Several mechanisms have been proposed to explain how
chemical antiozonants protect rubber. The scavenging mechanism, the protective film mecha-
nism or a combination of both are nowadays the most accepted mechanisms.
The scavenging mechanism states that antiozonants function by migrating towards the sur-
face of the rubber and, due to their exceptional reactivity towards ozone, scavenge the ozone
before it can react with the rubber.83 The scavenging mechanism is based on the facts that all
antiozonants react much more rapidly with ozone than do the double bonds of the rubber mole-
cules. This fact distinguishes antiozonants from antioxidants.
Studies of the reaction rates of various substituted paraphenylene diamines (PPDA’s)
towards ozone show that their reactivities are directly related to the electron density on the nitro-
gens due to the different substituents. Reactivity decreases in the following order: N,N,N’,N’-
tetraalkyl- > N,N,N’-trialkyl- > N,N’-dialkyl- > N-alkyl-N’-aryl- > N,N’-diaryl.84 It should be
noted, that their ease of oxidation decreases in the same order. As expected, PPDA’s (para pheny-
lene diamines) substituted by normal, secondary, and tertiary alkyl groups all exhibit essentially
the same reaction rates. Only the initial reaction of the antiozonant with the ozone is rapid; the
resulting ozonized products always react much more slowly. Thus the number of moles of ozone
absorbed by a compound is not necessarily an indication of its effectiveness. It is only the rate of
reaction which is important.
By itself, the scavenging mechanism suffers from a number of shortcomings. According to
this mechanism, the antiozonant must rapidly migrate to the surface of the rubber in order to
scavenge the ozone. However, calculations show that the rate of diffusion of antiozonants to the
rubber surface is too slow to scavenge all the available ozone.85 Many compounds, which react
very rapidly with ozone and therefore should be excellent scavengers, are not effective. A good
example is the poor activity of N,N’-di-n-octyl-PPDA (DnOPPD) compared to the excellent
activity of its sec-octyl isomer, DOPPD.36 Since these isomers have the same reactivity towards
ozone, the same solubility in rubber, the same molecular weight (and diffusion rates) and melt-
464 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

ing points (both are liquids), the difference in their antiozonant activities must reside in the nature
of their ozonized products.
The protective film mechanism states that the rapid reaction of ozone with the antiozonant
produces a film on the surface of the rubber, which prevents attack on the rubber, like waxes are
doing.86 This mechanism is based on the fact that the ozone uptake of elongated rubber contain-
ing a substituted p-phenylene diamine type of antiozonant is very fast initially and then decreas-
es rather rapidly with time and eventually stops almost completely. The film has been studied
spectroscopically and shown to consist of unreacted antiozonant and its ozonized products, but
no ozonized rubber is involved.87 Since these ozonized products are polar, they have poor solu-
bility in the rubber and accumulate on the surface.
Currently, the most accepted mechanism of antiozonant action is a combination of scaveng-
ing and protective film formation. Based on this mechanism, one concludes that the higher crit-
ical elongation exhibited by DOPPD is due to the nature of the protective film which forms while
scavenging ozone. The only way a film or coating can increase critical stress is, if it completely
prevents ozone from reaching the surface. Only a continuous flexible film can do this. For exam-
ple, wax forms such a protective but non-flexible film and increases the critical elongation.88 A
continuous flexible film also explains why DOPPD does not increase the critical elongation
under dynamic conditions. In this case, flexing would disrupt the continuity of the film and
destroy its ability to completely coat the rubber surface, just as flexing destroys the effectiveness
of waxes. It also explains why DOPPD does not increase the critical elongation in NBR89. In
NBR very little DOPPD is found on the surface. Consequently, any film, which forms on the sur-
face, is too thin to be effective. The difference in the amount of DOPPD on the surface of NBR
compared to SBR is attributed to the higher solubility of DOPPD in NBR.
The effect of ozone and DOPPD concentrations on critical stress can be explained by con-
sidering the factors involved in film formation and destruction. At a fixed ozone concentration,
increasing the concentration of DOPPD will increase the critical elongation because the equilib-
rium concentration of DOPPD on the surface of the rubber increases with loading. This results
in the formation of a thicker, more durable and flexible film. The higher equilibrium surface con-
centration of DOPPD, lying just below the film, also guarantees that any of the film destroyed
by ozone will be efficiently repaired before cracks can form. On the other hand, increasing the
ozone concentration at a fixed DOPPD level decreases the critical stress because the film reacts
and is too rapidly destroyed by ozone, to be repaired. Thus, the critical elongation will be that
point, where the ozone concentration destroys the film more quickly than that it can be repaired.
At very high ozone levels, this barrier is so quickly destroyed that the critical stress is the same
as the value for an unprotected stock. Since N-isopropyl-N’-phenyl-p-phenylenediamine (IPPD)
does not increase critical elongation, its reaction products with ozone must form a barrier which
contains many flaws. Indeed, IPPD is known to give a powdery bloom. However, combining
IPPD with waxes results in a dramatic increase in the critical stress. This has been attributed to
the ability of IPPD to facilitate wax migration and increase the thickness and continuity of the
wax bloom.90

Protection Against Ozone by Substituted PPD’s. — The most effective antiozonants are the
substituted PPD’s. Their mechanism of protection against ozone is based on the ‘scavenger-pro-
tective film’ mechanism.91-93 The reaction of ozone with the antiozonant is much faster than the
reaction with the carbon-carbon double bonds of the rubber on the rubber surface.79 The rubber
is protected from the ozone attack till the surface antiozonant is depleted. As the antiozonant is
continuously consumed through its reaction with ozone at the rubber surface, diffusion of the
antiozonant from the inner parts to the surface replenishes the surface concentration to provide
the continuous protection against ozone. A thin flexible film developed from the
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 465

antiozonant/ozone reaction products on the rubber surface also offers protection.

In a PPD molecule, the aryl alkyl-substituted NH group is more reactive towards ozone than
the bisaryl-substituted NH group owing to the higher charge density on the N-atom of the aryl
alkyl-substitute.94 This correlates very well with the literature report that aryl alkyl-PPD (e.g.,
6PPD) produced nitrone, while the bisalkyl-PPD such as 77PD [N,N’-Bis(1,4-dimethylpentyl)-
p-phenylenediamine] produced dinitrone instead.91,92 Apparently, the stabilizing effect of the N-
aryl group on the nitrone retards further reaction of the nitrone with ozone. A simplified reaction
mechanism for the aryl-alkyl PPD’s such as 6PPD is depicted in Figure 19.

FIG. 19. — Ozonation mechanism for aryl-alkyl-PPD's.70

Methods of Studying the Ozone Resistance of Rubber. — Since ozone attack on rubber is
essentially a surface phenomenon, the test methods involve exposure of the rubber samples under
static and/or dynamic strain, in a closed chamber at a constant temperature, to an atmosphere
containing a given concentration of ozone. Cured test pieces are visually examined periodically
for cracking. The length and amount of cracks is assessed according to the Bayer method.95,96
The ISO standard ozone test conditions involve a test temperature of 40 ± 1 °C and an ozone level
of 50 ± 5 pphm (parts per hundred million), with a test duration of 72 hours. Testing is done
under static95 and/or dynamic strain.96 These are accelerated tests and should be used for the rel-
ative comparison of compounds, rather than for the prediction of long-term service life. The
method is rather complicated and demands a long duration of ozone exposure. Therefore, in
some cases the rate constants of the antiozonants reaction with ozone in solution are used instead
to evaluate the efficiency of different antiozonants.97
The loss of antiozonants, either in a chemical or physical manner, appears to be the limiting
factor in providing long-term protection of rubber products. That is why for new antiozonants not
only the efficiency of the antiozonants must be evaluated, but one also has to watch other prop-
erties which influence their protective functions in an indifferent manner. For example, the mol-
ecule’s mobility, their ability to migrate, is one of the parameters determining the efficiency of
antiozonant action. Determination of the mobility kinetics of antiozonants can be done with a
gravimetric method elaborated by Kavun.98 This method was used to determine the diffusion
coefficient of several substituted PPD’s, in different rubbers and at different temperatures.99 The
diffusion coefficients were calculated using the classical diffusion theory: Table XXI. The diffu-
466 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

sion coefficients increase with increasing temperature and with decreased compatibility with the
rubber. The lower diffusion coefficient observed for SPPD (N-(1-phenylethyl)-N’-phenyl-p-
phenylenediamine) compared to that of IPPD and 6PPD was explained by an increased molecu-
lar weight and/or increased compatibility with the rubbers.

TABLE XXI
DIFFUSION COEFFCIENTS FOR IPPD, 6PPD AND SPPD (SEE FIGURE 26),
IN DIFFERENT RUBBERS AND AT DIFFERENT TEMPERATURE99

Rubber Temperature D [cm2/s]

IPPD 6PPD SPPD
NR/BR 10°C 1.16E-8 7.82E-9 6.56E-9
25°C 2.99E-8 1.92E-8 1.54E-8
38°C 6.89E-8 4.55E-8 3.58E-8
62°C 1.88E-7 1.47E-7 1.20E-7
85°C 3.51E-7 2.79E-7 2.17E-7
NR 10°C 3.40E-9 1.70E-9 1.30E-9
38°C 2.56E-8 1.39E-8 1.11E-8
62°C 1.19E-7 7.05E-8 6.05E-8
85°C 3.11E-7 2.34E-7 1.66E-7
SBR1500 38°C 1.03E-8 6.13E-9 4.62E-9
62°C 4.28E-8 3.05E-8 2.47E-8
85°C 1.36E-7 9.72E-8 6.02E-8
BR 38°C 1.32E-7 8.56E-8 6.79E-8
62°C 2.71E-7 1.99E-7 1.64E-7

6. Mechanism of Protection Against Flex Cracking. — Flex cracking, the occurrence and
growth of cracks in the surface of rubber when repeatedly submitted to a deformation cycle, is
determined by fatigue testing. Fatiguing of rubbers at room temperature is a degradation process
caused by repeated mechanical stress under limited access of oxygen. The mechanical deforma-
tion stress is believed to generate macroalkyl radicals (R•). A small fraction of the macroalkyl
radicals reacts with oxygen to form alkylperoxy radicals, still leaving a high concentration of the
macroalkyl radicals. Consequently, removal of the macroalkyl radicals in a catalytic process con-
stitutes a prevailing anti-fatigue process.32 On the other hand, the macroalkyl radicals are rapid-
ly converted to the alkylperoxy radicals under air-oven heat aging. The auto-oxidation propagat-
ed by the alkylperoxy radicals thus dominates the degradation process. Therefore, removal of the
alkylperoxy radicals becomes the primary function of an antioxidant.
It has been shown that diarylamines are good anti-fatigue agents and that diarylamine nitrox-
yl radicals are even more effective than the parent amines. The anti-fatigue mechanism of the
amine anti-degradants, shown in Figure 8, has been proposed where the formation of the inter-
mediate nitroxyl radical plays an active role.100 Generation of nitroxyl radicals from the free
amines is depicted in Figure 20. In the fatigue process, macroalkyl radicals are generated and
subsequently removed by reaction with these nitroxyl radicals. The resulting hydroxylamine can
be re-oxidized by alkylperoxy radicals to re-generate the nitroxyl radicals in an auto-oxidation
chain-breaking process.
The nitroxyl radicals can be partially converted back to the free diarylamine during vulcan-
ization through the reductive action of thiyl radicals of thiols. The free diarylamine thus regen-
erated, would repeat the reaction described in Figure 20 to form more nitroxyl radicals.
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 467

7. Trends Towards Long-Lasting Antidegradants.

FIG. 20. — Anti-fatigue mechanism of diaryl amines.

Introduction. — Antidegradants are very important compounding additives in their role to

economically maintain rubber properties at service conditions. Although conventional anti-
degradants such as 6PPD and IPPD provide protection against oxygen and ozone, this protection
is of short duration (1-5 years, depending on the service conditions). Producers of rubber chem-
icals are focussing on new developments, addressing longer and better protection of rubber prod-
ucts.101 Therefore, several new types of long-lasting antioxidants and long-lasting antiozonants
(5-15 years, depending on the service conditions) have been developed over the last two decades.

Long-Lasting Antioxidants. — To limit the thermal oxidative deterioration of elastomers and

their vulcanizates during storage, processing, and use, different systems of antioxidants are used.
The activity of the antioxidants depends on their ability to trap peroxy and hydroperoxy radicals
and their catalytic action in hydroperoxide decomposition. Their compatibility with the polymers
also plays a major role. Moreover, it is very important to limit antioxidant loss by extraction
(leaching) or by volatilization. Food packaging and medical devices are areas in which additive
migration or extraction is of major concern. Contact with oils or fats could conceivably lead to
ingestion of mobile polymer stabilizers. In an effort to address this concern, the U.S. Food and
Drug Administration (FDA) has set a code of regulations governing the use of additives in food
contact applications.102 These regulations contain a list of acceptable polymer additives and dose
limits for polymers, which may be used for specific food contact. Inclusion of a particular com-
pound in this list depends both on specific extractability and toxicological factors. Obviously,
polymer bound stabilizers cannot be extracted and would therefore prevent inadvertent food con-
tamination. An additional consideration is the effect of additive migration on surface properties.
As additives migrate or bloom to the polymer surface, the ability to seal or coat the surface may
deteriorate. This affects coating adhesion and lamination peel strength.
468 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

The above-described issues are the reasons for an increased interest in the synthesis of new
antioxidants with the possibility to graft to the polymer backbone or to form polymeric or
oligomeric antidegradants. In the last two decades, several approaches have been evaluated in
order to develop such new antioxidants:
• Attachment of hydrocarbon chains to conventional antioxidants in order to increase the
MW and compatibility with polymers;103
• Polymeric or oligomeric antioxidants;04
• Polymer bound or covulcanizable antioxidants;105-107
• Binding of several functional groups onto a single platform.108
Examination of the history of antioxidants such as hindered phenols and amines shows a
move from low molecular weight products to higher molecular weight products. Specifically,
polymer industries have abandoned the use of e.g. butylated hydroxy toluene (BHT) in favor of
tetrakismethylene (3,5-di-t-butyl-4-hydroxydrocinnamate)methane (see Figure 21). Likewise,
polymeric HALS, like poly-methylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)piperidinyl] siloxane,
replaced the low molecular weight hindered amine Lowilite 77 (see Figure 22). The next obvi-
ous step was to produce a new class of stabilizers, which are chemically bound to the polymer
chain. This approach has had varying degrees of success. While the extraction resistance of the
bound stabilizers was significantly improved, performance suffered greatly. Because degradation
processes may occur in localized portions of the bulk of the polymer, mobility of the stabilizer
plays a key role in antioxidant activity.

FIG. 21. — Replacement of low Mwt. phenolic AOx by high Mwt. product.

The antioxidative activities of polymeric antioxidants prepared from Verona oil and the con-
ventional phenolic antioxidant 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (DTBH),
chemically grafted to polystyrene and polyurethanes, is similar and in some cases even better
than that of the corresponding low molecular weight phenolic antioxidants.104
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 469

FIG. 22. — Replacement of lowMWt HALS by high MWt product.

Several ways of obtaining polymer-bound antioxidants have been described. Roos and
D’Amico reported polymerizable p-phenylene diamine antioxidants.109,110 Cain et al. reported
the ‘ene’ addition of nitrosophenols or aniline derivatives to produce polymer bound stabiliz-
ers.111 The most versatile method of preparation of bound antioxidant is by the direct reaction of
a conventional antioxidant with a polymer. Scott et al. have demonstrated that simple hindered
phenols, which contain a methyl group in the o- or p-position, can react with natural rubber in
the presence of oxidizing free radicals to yield polymer bound antioxidants.112 The antioxidants,
like styrenated phenol, diphenylamine etc. bound to hydroxyl terminated liquid natural rubber by
modified Friedel-Craft’s reactions were found to be effective in improving the aging resist-
ance.113 PPD’s bound to natural rubber showed improved aging resistance compared to conven-
tional PPD’s, but as expected a worse ozone resistance because the antidegradants cannot migrate
to the surface.105. Quinone diimines (QDI) have been reported as bound antioxidant and diffus-
able antiozonant. During vulcanization, part of the QDI is grafted to the polymer backbone and
acts as bound antioxidant, whereas the other part is reduced to PPD and is active as diffusable
antiozonant.106
The protection efficiency of antioxidant couples consisting of a classical compound (disub-
stituted p-phenylenediamines and dihydroquinoline derivatives) and compounds with a disulfide
bridge, resulting from diamine and phenolic structures, was reported by Meghea and
Giurginca.107 Antioxidants containing a disulfide bridge are able to graft onto the elastomer chain
during processing and curing, leading to a level of protection superior to the classical anti-
degradants.
One of the latest developments in stabilizers is with polysiloxanes, which provide flexible,
versatile backbones for a variety of classes of polymer stabilizers. The siloxanes appear to be
good backbones, because they are rather inexpensive, easily functionalized, have a high level of
functional sites, good compatibility with many polymers and excellent thermo and photolytic sta-
bility.108 Hindered amines, hindered phenolics and metal deactivators have been grafted onto the
polysiloxanes. The low extractability of siloxane based additives was further enhanced by the
inclusion of graftable pendant groups onto the polysiloxane backbone.114 The grafted stabilizers
maintain their activity due to the flexible siloxane platform. This was seen as a limitation of
monomeric stabilizers, which have been grafted onto the polymer matrix and thus are not mobile
at all.
There is a clear demand for long-lasting, non-staining and non-discoloring antiozonants for
better appearance products such as tire sidewalls. The functional classes of antiozonants include
substituted monophenols, hindered bisphenols and thiobisphenols, substituted hydroquinones,
organic phosphites, and thioesters.25 Triphenyl phosphine, substituted thioureas and isothioureas,
470 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

thiosemicarbazides, esters of dithiocarbamates, lactams, olefinic and enamine compounds are

reported as non-staining antiozonants.115,116 Approaches to completely replace the PPD’s with a
non-discoloring antiozonant have had only limited success, leading to the development of new
classes of non-staining antiozonants.
Warrach and Tsou138 reported that bis-(1,2,3,6-tetrahydrobenzaldehyde)-pentaerythrityl
acetal provides superior ozone protection for polychloroprene, butyl rubber, chlorobutyl and bro-
mobutyl rubbers relative to p-phenylenediamine antiozonants, without discoloring the rubber or
staining white-painted steel test panels. However, the ozone resistance of diene elastomers (nat-
ural rubber, polyisoprene, styrene-butadiene rubber, polybutadiene, nitrile rubber) or inherently
ozone-resistant elastomers (ethylene-propylene copolymers, ethylene-propylene-diene terpoly-
mers, chlorosulfonated polyethylene, ethylene vinylacetate) is not improved by this compound.

FIG. 23. — Tetrahydro-1,3,5-tri-n-butyl-(S)-triazinethione.

Rollick, Gillick and Kuczkowski115-117 reported a new class of antiozonants for rubber that
do not discolor upon exposure to oxygen, ozone or ultraviolet light, namely triazinethiones. Only
changes in substitution on the nitrogen adjacent to the thiocarbonyl group affected their antiozo-
nant efficiency. Accelerated weatherometer aging of a titanium dioxide/treated-clay filled
styrene-butadiene rubber compound showed their non-discoloring nature. Use of 4 phr tetrahy-
dro-1,3,5-(n)-butyl(S)-triazinethione (Figure 23) resulted essentially in no change in colour,
whereas use of only 1phr of N-(1,3-dimethylbutyl)-N’-phenyl-para-phenylenediamine signifi-
cantly discolored the rubber compared to the control,Table XXII). The triazinethiones provided
a significant degree of ozone protection to a natural rubber / butadiene rubber black sidewall
compound. They are reported as particularly valuable for use in light-colored stocks.
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 471

TABLE XXII
WEATHEROMETER INDUCED DISCOLORATION OF 6 PPD AND TBTT CONTAINING SBR115
Antiozonant a) Hours L A b ΔE b)
None 24 89.89 0 7.78
48 89.61 -0.10 10.19
96 89.72 -0.10 11.90
1phr 6PPD c) 24 34.21 3.69 8.21 55.80
48 40.25 2.47 7.93 49.48
96 45.93 1.86 8.40 43.97
4phr TBTT d) 24 86.66 0.80 10.28 4.09
48 87.81 0.81 10.99 2.17
96 87.52 1.01 11.49 2.50
a) Formulation: 100 phr SBR 1502, 30 phr titanium dioxide, 30 phr mercaptosilinated clay, 10 phr ZnO, 5 phr naphthenic
oil, 2 phr stearic acid, 2 phr sulphur, 0.25 phr TMTD (tetramethyl thiuram disulfide).
b) DE = ÷((DL)2+(Da)2+(Db)2) = change in whiteness (DL), hue (Da) and chroma (Db) upon aging.
c) N-(1,3-Dimethylbutyl)-N’-phenyl-para-phenylenediamine.
d) Tetrahydro-1,3,5-tri-(n)-butyl-(S)-triazinethione.

Ivan, Giurginca and Herdan118 reported that 3,5-di-tert-butyl-4-hydroxybenzylcyanoacetate

is a non-staining antiozonant that affords similar protection to natural rubber and to cis-polyiso-
prene compounds as provided by N-isopropyl-N’-phenyl-para-phenylenediamine (see Figure
24). This product lasts longer than conventional non-staining antiozonants, like the styrenated
phenols.

FIG. 24. — 3,5-di-tert-butyl-4-hydroxybenzyl cyanoacetate.

Wheeler119 described a new class of non-staining antiozonants, namely the tris-N-substitut-

ed-triazines. 2,4,6-Tris-(N-1,4-dimethylpentyl-para-phenylenediamino)-1,3,5-triazine (Figure
25), gave excellent ozone resistance in a natural rubber / butadiene rubber compound when com-
pared to N-(1,3-dimethylbutyl)-N’-phenyl-para-phenylenediamine, but without contact, migra-
tion or diffusion staining (Table XXIII). Hong120 reported equal dynamic ozone performance of
this triazine antiozonant to the PPD’s in both natural rubber and butadiene rubber compounds.
Birdsall, Hong and Hajdasz121 described that the triazine antiozonant formed a discoloring
bloom on a natural rubber / butadiene rubber compound, but that the bloom was minimal when
compounded at two phr or lower levels. When used in combination with a PPD, better ozone pro-
tection is obtained compared to using the triazine antiozonant alone, at the same total level of
antiozonant. The combination PPD and triazine antiozonant provides longer-term protection.122
472 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

FIG. 25. — 2,4,6-Tris-(N-1,4-dimethlpentyl-para-phenylenediamino-)1,3,5-triazine (TAPTD).

TABLE XXIII
STAINING EXPERIMENTS a) OF THE TRIAZINE ANTIOXIDENT119
Method Antiozonant L
A. Contact stain Blank 87.10
after 96 hours TAPDT b) 83.77
HPPD c) 65.59
B. Migration stain Blank 86.89
after 96 hours TAPDT b) 87.53
HPPD c) 77.79
C. Diffusion stain, exposed to Blank 88.10
sunlamp 4 hours at 328 °K TAPDT b) 82.42
HPPD c) 32.65
a) Tests were carried out as designated in ASTM Method D-925-83 related to staining of surfaces by contact, migration,

or by diffusion. Hunter color values were measured on the L-scale. On this scale 100 is white and 0 is black.
b) Tris-(N-1,4-Dimethylpentyl-para-phenylenediamino)-1,3,5-triazine.
c) N-(1,3-Dimethylbutyl)-N’-phenyl-para-phenylenediamine.

Lehocky, Syrovy and Kavun99 reported the migration rates of IPPD, 6PPD and SPPD
(Figure 26), determined in different polymers and at different temperatures. SPPD showed the
lowest migration rate and is therefore expected to last longest in rubber compounds, Table XXI.
However, the importance of the migration rate should not be overestimated, as the value is not
sufficient to determine the effect and the efficiency of the antiozonant.

FIG. 26. — Structure of SPPD (N-(1-phenylethyl)-N'-phenyl-p-phenylenediamine.

 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 473

The most prevalent approach to achieve long-lasting and non-staining ozone protection of
rubber compounds is to use an inherently ozone-resistant, saturated-backbone polymer in blends
with a diene rubber. The ozone-resistant polymer must be used in sufficient concentration (min-
imum 25 phr) and must also be sufficiently dispersed to form domains that effectively block the
continuous propagation of an ozone-initiated crack through the diene rubber phase within the
compound. Elastomers such as ethylene-propylene-diene terpolymers, halogenated butyl rub-
bers, or brominated isobutylene-co-para-methylstyrene elastomers have been proposed in com-
bination with natural rubber and / or butadiene rubber.
Ogawa, Shiomura and Takizawa123,124 reported the use of various EPDM polymers in blends
with natural rubber in black sidewall formulations. Laboratory testing showed improved resist-
ance to crack growth and thermal aging.
Hong125 reported that a polymer blend of 60 phr of natural rubber and 40 phr of EPDM rub-
ber afforded the best protection of a black sidewall compound to ozone attack. Use of a higher
molecular weight EPDM rubber gave good flex fatigue-to-failure and adhesion to both carcass
and tread compounds. TAPDT mixed with the natural rubber to form a masterbatch followed by
blending with the EPDM rubber and other ingredients, afforded the most effective processing in
order to protect the natural rubber phase. Compounds containing this natural rubber/EPDM rub-
ber blend (60/40) with 2.4 phr of the triazine antiozonant passed all requirements for the tire
black sidewall.
Sumner and Fries126 reported that ozone resistance is depended on the level of the EPDM
rubber. When using 40 phr of EPDM rubber in the compound there is no cracking throughout the
life of the black sidewall. Ozone resistance also depends on proper mixing of the EPDM rubber
with natural rubber in order to achieve a polymer domain size of less than one micron. Otherwise
cracking can be severe. The combination of high molecular weight and high ethylidene nor-
bornene (ENB) content afforded good adhesion to highly unsaturated polymers. The adhesion
mechanism involves the creation of radicals when long chains of EPDM rubber and natural rub-
ber are broken down by shearing and mechanical work. Grafting between the two elastomers is
believed to occur. The graft polymer is thought to act as compatibilizer. The natural
rubber/EPDM rubber compound does not rely on migration of antidegradants to achieve ozone
resistance and therefore does not stain the sidewall. Appearance is excellent throughout the serv-
ice life of the tire. However, at the current stage of development, natural rubber/EPDM rubber
sidewall compounds are difficult to mix, too expensive, result in an increased rolling resistance
and have a reduced tack compared to natural rubber/butadiene rubber sidewall compounds.
Related work carried out by Polysar in this field is described in detail.127-137
As a general view on antidegradant activity with respect to type, structures etc., authors
would like to refer to the references described below. Antidegradants are divided into staining
and non-staining products, with or without fatigue, ozone and oxygen protection. The most
commonly used antidegradants for general-purpose rubbers were reported by Huntink, Datta and
Noordermeer.139

8. Protection Against Degradation in Oxidative Aging Environments. — One of the burning

demands in the rubber industry has been to reduce the changes in the network during the service
life of rubber components. In a broad sense, this is also considered as degradation (reversion) of
network but under oxidative environments. The changes in the network under aerobic conditions
are different in nature than experienced under anaerobic conditions. In a true sense, the rubber
compounds experience hardening effects in the presence of oxygen and heat.
The process of hardening or increase in modulus or increase in crosslink density is a result
of oxidation of sulfidic crosslinks, liberation of active sulfur and consequently re-crosslinking.
The process in schematically shown in Figure 27.
474 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

FIG. 27. — Reaction of monosulfides with oxygen/heat forming additional crosslinks.

It is well known that the degradation of polysulfides is catalyzed by the presence of accel-
erators (Figure 28). The liberated active sulfur is responsible for introduction of additional
crosslinks and hence increases in modulus.

FIG. 28. — Reaction of polysulfides with oxygen/heat forming additional crosslinks.

 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 475

In order to reduce the unwanted hardening effects during oxidative aging, the trapping or
removal of accelerator fragments is desirable. Over the years, focus was on the development of
an accelerator, which becomes inactive after the vulcanization and thereby decreases the kinet-
ics of degradation of polysulfides. The research culminated in a development of a novel acceler-
ator, N-Cyclohexyl-4,6-Dimethyl-2-pyrimidine Sulfenamide.140

CDMPS has been tested in several compounds where the effect on modulus increase during
oxidative ageing is monitored. Some typical data are shown in Table XXIV.

TABLE XXIV
SUMMARY OF ADVANTAGE OF CDMPS OVER CONVENTIONAL ACCELERATOR
SBR-BR Passenger Tread
(Summary)
Rheo; 160 °C Control CDMPS
Delta S, Nm 1.14 1.15 Control CDMPS
Ts2, min 10 12 CBS 1.3 0
t90, min 4.3 4.5 CDMPS 0 1.3
MBT 0 0.5
Cure: 160°C/t90 Sulfur 2 2
(Changes after aging a)) 3d/100°C
Hardness, IRHD +11 +6
MSa) (based on M200%), % +220 +158
Elongation drop,% -39 -22
Flex, % (Constant stress) -35 -10
Tangent delta, -20°C, % -20 -3
Masterbatch: SBR 1712, 137.5; N-220, 60; zinc oxide, 3.0; stearic acid, 2.0; 6PPD, 1.0
a) MS, %= (Aged M200 / Unaged M200) X 100.

It is clear from the data that the changes in hardness and modulus during oxidative ageing
are considerably reduced. The resistance to hardness increase positively influences the dynamic
properties as shown in Table XXIV.
In order to understand the changes in the network during oxidative ageing in the presence of
CDMPS, some network studies were carried out. Data are tabulated in Table XXV.
476 RUBBER CHEMISTRY AND TECHNOLOGY VOL. 80

TABLE XXV
CROSSLINK DENSITY (CURE: 160 °C/t90)
XL-densities a) X 105 Control CDMPS
Unaged
Total 3.79 3.82
Poly-S 1.95 2.08
Di-S 0.53 0.56
Mono-S 1.31 1.18
ZnS X 102 0.550 0.540
Aged, 3d/100 °C
Total 5.15 4.30
Poly-S 0.64 1.05
Di-S 0.15 0.30
Mono-S 4.36 2.95
ZnS b) X 102 0.587 0.727
a) Crosslink density expressed in gram mole/gram rubber hydrocarbon.
b) Zinc sulfide sulfur expressed in gram/gram rubber hydrocarbon.

The increase in crosslink density upon oxidative ageing is minimized in the presence of
CDMPS. The level of zinc sulfide is higher indicating that part of the sulfur kicked out during
the ageing process is trapped by zinc as zinc sulfide. The mechanism of the process is proposed
as shown in Figure 29.

FIG. 29. — Formation of zinc sulfide and trapping of accelerator’s residue.

CDMPS has also been tested in high sulfur skim , NR/BR tread as well as S-SBR silica
treads. The advantages are well confirmed in all applications.

9. Recent Developments with Sulfron 3000. — Recently,141-144 Teijin Twaron has introduced
modified Aramid called Sulfron, which is effective in sulphur vulcanized systems claiming to
reduce hysteresis and maintaining hysteresis during oxidative ageing of the vulcanizates. Table
XXVI summarizes some oxidative resistance data in the presence of Sulfron 3000.
 RUBBER VULCANIZATES DEGRADATION AND STABILIZATION 477

TABLE XXVI
MAINTENANCE OF HYSTERESIS DURING AEROBIC AGING IN THE PRESENCE OF SULFRON 3000

Stocks Conditions G’, MPa G”, MPa Tan δ % change

Control Unaged 3,61 0,446 0,1235
Aged 2d 5,67 0,775 0,1366
Aged 3d 6,71 0,980 0,1460 18
+Sulfron 3000 Unaged 4,10 0,430 0,1048
(1, 0phr) Aged 2d 5,20 0,550 0,1057
Aged 3d 5,77 0,630 0,1091 5
+Sulfron 3000 Unaged 4,25 0,454 0,1068
(1, 5phr) Aged 2d 5,48 0,595 0,1085
Aged 3d 5,88 0,650 0,1105 4

All the processes described in this article provide a bird's eye view of degradation and the
means to overcome this unwanted phenomenon.

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[ Received April 2007 ]