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Multifunctional Acrylates as Anti-Reversion

Agents in Sulfur Cured Systems

Steven K. Henning* and Scott A. Shapot


Presented at the Fall 168th Technical Meeting
of the Rubber Division, American Chemical Society
Pittsburgh, PA
November 1-3, 2005

*Speaker

Cray Valley USA, LLC Oaklands Corporate Center

468 Thomas Jones Way, Suite 100

877-US1-CRAY (877-871-2729)
5522 07/11

Web: www.crayvalley.com

Exton, PA 19341

ABSTRACT

The dynamic nature of polysulfidic bonds characterizes


the utility of the system, but also facilitates reversion.
Reversion is defined by a loss in physical properties
associated with degradation of network integrity. The
reversion process is thermally initiated and primarily
associated with overcure or high temperature service
conditions. Reversion involves reactions that lead to
the desulfuration of polysulfidic linkages and main-chain
modification (cis-to-trans isomerization) which results
in weaker network structures.5,6 As desulfuration
progresses, the distribution shifts from polysulfidic to
mono- and di-sulfidic crosslinks and eventually
crosslink density is also lost. The result is a degradation
of physical properties and a decrease in the
performance of the rubber article.7

Multifunctional acrylates have found utility as effective


anti-reversion agents in sulfur cured applications where
overcure or high temperature cure conditions exist. It
has also been demonstrated that certain zinc salts of
methacrylic acid reduce reversion. In this paper,
commercially available multifunctional acrylates are
evaluated in both conventional and semi-EV sulfur
cured systems with the reversion resistance and cured
physical properties of the resulting natural rubber/
carbon black vulcanizates compared to other
commercially produced agents.
It will be shown that the multifunctional acrylate (Cray
Valley SR534) provides excellent reversion
resistance. In addition, this anti-reversion agent
demonstrates the least change in physical properties
when overcure conditions are induced.

Many strategies have been developed to prevent the


reversion process. Reversion can be minimized in cure
systems which promote mono- and di-sulfidic
crosslinks. Sulfur-donor systems or polysulfide
polymers can be utilized.8 It has recently been
proposed that certain zinc methacrylate salts, when
used as activators in accelerated sulfur vulcanization,
promote crosslinks of lower sulfur rank and minimize
reversion.9 These attempts to mediate reversion also
alter the original structure of the network itself, typically
decreasing dynamic and tear properties that are the
direct benefits of polysulfidic linkages.

Data will be provided demonstrating the unique


properties of acrylates including reversion resistance,
retention of physical properties and crosslink density
as a function of reversion, viscoelastic properties,
flexural fatigue results, and the optimization of antireversion agent level in a model natural rubber
compound.
INTRODUCTION

Alternately, the inclusion of more stable crosslinks in


addition to the sulfur network has been proposed.10
Similarly, the mixing of peroxide and conventional
accelerated sulfur cure systems has been attempted.11
A disadvantage of this compounding method is the need
to reformulate in order to compensate for the new,
structurally different crosslinks in order to maintain the
desired cured properties.

Physical properties of vulcanized rubber systems are


influenced by the curing process and chemical nature
of the formed crosslinks. The bond strength of linkages
can help predict the performance of a given vulcanizate
in specific applications. Peroxide cured systems are
often employed in static or compressive conditions
where low set and heat resistance are required. A
network derived from polysulfidic linkages is preferred
for components subject to dynamic strain where
improved flexural fatigue and tear properties are
desired. Bond dissociation energies are often used to
quantify the strength of the crosslinks and differentiate
the systems.1,2 Carbon-carbon linkages possess high
dissociation energies and resist failure to a limiting point,
then fail catastrophically. Having lower dissociation
energies, polysulfidic bonds break more readily under
strain, but due to their chemical nature also possess
the ability to reform and alleviate stresses.3,4

A more popular approach is to compensate for the


destruction of crosslinks by adding chemical additives
that react when reversion processes are initiated. In
such systems, the desulfuration mechanism is offset by
the formation of new, stable crosslinks. Ideally, the
processes have similar rates such that crosslink density
is maintained. It has been shown that acrylate esters
are effective anti-reversion agents that display this
behavior.12 Earlier work has also demonstrated the
utility of acrylates to improve the heat-aged properties
3

of rubber compounds, suggesting a similar


mechanism.13

Using an internal mixer, a non-productive masterbatch


was prepared containing all ingredients except antireversion agents and curatives. Table II outlines the
formulation used for the masterbatch and the specific
cure packages. Conventional (CV), semi-efficient (SEV), and efficient (EV) vulcanization systems were
evaluated. These are model formulations that have not
been optimized for a specific application. The
productive stage was mixed using a two-roll mill.
Milling times were approximately 5 minutes. Productive
stock was aged overnight prior to testing.

The present study evaluates the performance of a


multifunctional acrylate ester product (Cray Valley
SR534) specifically optimized to prevent reversion in
rubber compounds. SR534 is compared to the imidebased
anti-reversion
agents
1,3bis(citraconimidomethyl)benzene and N,N-mphenylenedimaleimide. The former compound has
been promoted as capable of crosslink compensation
reactions,14 while the latter is commonly used as a
secondary accelerator. Cure characteristics and antireversion properties will be compared. Tensile,
viscoelastic, and flexural fatigue properties are
evaluated. Special attention is placed on comparing
the efficiency with which the various additives maintain
physical properties as a function of reversion.

Physical Testing
The determination of vulcanization behavior was
performed on a Tech Pro MDPT moving die rheometer
(MDR) according to ASTM D 5289. Cure temperature
for sample preparation is 160C unless otherwise
noted. Reversion was calculated as the difference in
torque between the highest initial recorded value (MH)
and that at 60 minutes (M60). The individual calculated
t90 times (optimal cure) were used for subsequent test
sample preparation. In addition, reverted samples were
prepared by curing to 60 minutes. Stress-strain and
tear data was acquired on a Thwing-Albert Materials
Tester following ASTM D 412 and D 624 (Die C).
The MDR was also employed to evaluate both
unvulcanized and cured dynamic properties under
sinusoidal shear conditions at frequencies and
amplitudes defined later in the text. DeMattia flex
fatigue was determined according to ASTM D 813
under adiabatic conditions starting at room temperature.
Complete testing results are provided in Appendices I
and II.

EXPERIMENTAL
Chemicals
The compounds evaluated in this study are given in
Table I. The commercially available products were
used without further treatment or purification.
Table I. Anti-reversion agents.
Chemical Additive

Code

multifunctional acrylate ester


1,3-bis (citraconimidomethyl)benzene
N,N'-m- phenylenedimaleimide

SR534
CIMB
PDM

Rubber Compounding

Table II. Formulations.


Ingredient, phr
Non-Productive Natural Rubber (CV-60)

Productive

CV

S-EV

EV

100.0

100.0

100.0

Carbon Black (N 330)

50.0

50.0

50.0

Zinc Oxide

5.0

5.0

5.0

Stearic Acid

1.5

1.5

1.5

Antioxidanta

1.0

1.0

1.0

Anti-Reversion Agent

0, 2.0, 5.0 0, 2.0, 5.0 0, 2.0, 5.0

Sulfur

2.5

1.2

0.2

TBBSb

0.6

1.6

2.0

TMTDc
a

2.0

2,2,4-trimethyl-1,2-hydroquinoline
N-t-butylbenzothiazole-2-sulfena mide

b
c

tetramethylthiuram disulfide

Swelling Experiment

RESULTS AND DISCUSSION

Samples were mixed in a Brabender Prep Mixer using


the same formulation in Table II with the carbon black
omitted from the masterbatch. The unfilled compounds
were mixed for 4 minutes at 60 rpm and 60C. The
MDR was used to determine optimal cure times and
vulcanizates were prepared. Swelling experiments
were conducted on cylindrical samples of known
weight and dimensions. Crosslink density was
determined using the experimental methodology
outlined by Flory and Rhener1 and modified with
equivalent terms derived from theories of rubber
elasticity. The parameter used for the toluene/cispoly(isoprene) system was 0.37.

Model Formulation Development


In order to compare the given anti-reversion agents, it
is best to understand what formulation characteristics
contribute to the reversion process. Elastomers with
low degrees of unsaturation provide the least amount
of reversion, while reversion is promoted in unsaturated
rubber containing high allylic hydrogen content. Figure
1 correlates the extent of reversion as a function of
allylic hydrogen for a series of elastomers. The
formulation used was identical to Table II, substituting
various polymers (ethylene-propylene-diene
monomer, EPDM; emulsion styrene-butadiene rubber,
SBR; cis-butadiene rubber, BR; cis-isoprene rubber,
IR; natural rubber, NR).

60
MH-M60/MH (%)

NR
50

IR

40
30
BR
20
10
EPDM

SBR

0
0

Allylic Hydrogen / Monomer Unit

Figure 1. Reversion as a function of allylic hydrogen concentration.


It has been suggested that while the amount of sulfur
controls the overall reaction kinetics, the amount and
type of accelerator determines the overall length of
the sulfidic linkages.1,2 The sulfur-to-accelerator ratio
is used as a guideline for determining the type of cure
package in use and the distribution of sulfur crosslink
rank.3 Table III provides an outline of cure types, sulfurto-accelerator ratios, and typical crosslink distributions.

Table III. Cure types and bond distributions.


CV

S-EV

EV

Sulfur-to-Accelerator R atio

1 - 1.7

1.7 - 0.4

0.4 - 0.08

Polysulfidic %
Mono-, Disulfidic %

60-80
20-40

30-50
50-70

5-25
75-95

The rheometer cure profiles for the listed cure packages


are provided in Figure 2. It is clear that as the sulfurto-accelerator ratio decreases (CV to S-EV) reversion
was reduced. In an efficient vulcanization (EV), sulfur
donors are utilized and no reversion was evident.
Kinetic and cure state data from these vulcanizations
is provided in Table IV.

35

EV

30

Torque (dNm)

25

S-EV

20

CV

15
10
5
0
0

10

20

30

40

50

60

Time (minutes)

Figure 2. Vulcanization profiles of conventional (CV), semi-efficient (SE-V) and efficient (EV)
vulcanizations.
6

Table IV. Vulcanization data by cure type.

t2 (minutes)
t90 (minutes)
delta torque (dNm)
reversion (dNm)

CV

S-EV

EV

1.42
4.51
29.60
14.85

3.22
5.33
28.35
8.41

1.83
4.81
26.46
0

Reversion Resistance
SR534 is a multifunctional acrylate ester compound
that has been optimized for use in rubber
compounding. In a more traditional role as coagents
for peroxide cure systems, acrylate and methacrylate
esters are available in a wide range of structural
variation. SR534 was developed specifically to
address reversion resistance in sulfur vulcanized,
unsaturated rubber compounds. Figure 3 compares
the reversion resistance properties of SR534 to a
diacrylate (1,4-butanediol diacrylate) and
trimethacrylate (trimethylolpropane trimethacrylate) at
5 phr in the model formulation. SR534 is a blend of
selected multifunctional acrylates and outperforms the
diacrylate. The data demonstrates that the methacrylate
was also not effective, a finding reported in earlier
work.12 The diacrylate and trimethacrylate appeared
to limit cure (MH), while SR534 matched the
crosslinking efficiency of the control. Vulcanization
data is outlined in Table V. A higher torque value at
M60 compared to MH indicates marching modulus
and therefore no reversion.

Having the highest allylic hydrogen concentration, cis1,4 poly(isoprene) (synthetic and natural rubber)
displayed the greatest loss in crosslink density. In
addition, the data indicates that reversion was most
pronounced using a cure package which promotes
polysulfidic crosslinks. Therefore, model formulations
based on natural rubber using both CV and S-EV cure
systems have been selected to best evaluate the
behavior and efficiency of anti-reversion agents.

50
45

Torque (dNm)

40

control

35

SR534

30
25

1,4-Butanediol diacrylate

20

TMPTMA

15
10
5
0
0

10

20

30

40

50

Time (minutes)

Figure 3. Activity of SR534 versus diacrylate and trimethacrylate; 5 phr additive.

60

Table V. Reversion data for various agents.

phr

MH
(dNm)

M60
(dNm)

Re ve rsion
(dNm)

control

--

31.05

16.20

14.85

SR534
Diacrylate
Trimethacrylate

5
5
5

30.60
24.54
25.29

33.25
22.30
16.60

0
2.24
8.69

The use of acrylate ester products as coagents for


peroxide-cured systems is a major application, and
also demonstrates their ability to participate in freeradical initiated addition and grafting reactions.1 Given
the chemical environment of the model sulfur-cured
formulation, a crosslinking mechanism relying on
radical intermediates may be unlikely. Containing
acrylate ester functionality, the structure of SR534 is
fundamentally different than the imide-based products.
However, the ability to participate in similar crosslinking
reactions has also been proposed.2,3,4 Figures 4 and 5
provide a comparison of these agents in both the CV
and SE-V formulations, at 5 phr of additive and a cure
temperature of 160C. Table VI outlines the
vulcanization data in these formulations at both 2 and
5 phr of additive. It is shown that both SR534 and
CIMB provide similar rheological profiles that are
distinguished by a lack of reversion. Both additives
not only matched the MH of the control, but maintained
torque with time. PDM increased MH and lost
considerable torque during overcure.

The imide-based commercially available anti-reversion


agents PDM and CIMB were also evaluated in the
same formulation. The reported mode of activity for
CIMB is to compensate for the loss of crosslink
density as a function of reversion by generating
additional, non-sulfur crosslinks that are thermally
stable.10,14 A Diels-Alder reaction has been proposed.
PDM is a secondary accelerator also utilized for
reversion resistance, but is more active and leads to
the addition of non-sulfur crosslinks during the
vulcanization step through a similar reaction scheme.

60
50
Torque (dNm)

PDM
40

SR534

30

CIMB
20

control

10
0
0

10

20

30

40

50

60

Time (minute s)

Figure 4. Activity of SR534 compared to CIMB and PDM; CV formulation, 5 phr additive.

60

Torque (dNm)

50

PDM

40

SR534, CIMB

30
20

control

10
0
0

10

20

30

40

50

60

Time (minutes)

Figure 5. Activity of SR534 compared to CIMB and PDM; S-EV formulation, 5 phr additive.
reversion. CIMB has also been promoted to exhibit
this type of behavior. Its form differs from PDM by
altering the attachment and sterics of the imide structure,
favorably affecting the activity of the compound.
Similarly, SR534 was developed by designing a
structure that exhibits activity closely matching CIMB,
without incorporating amine structures.

As the most desirable aspects of sulfur-cured systems


are attributed to the polysulfidic nature of the crosslinks,
the addition of non-sulfur crosslinks during the initial
vulcanization step may be undesirable. Therefore,
SR534 was developed considering that an ideal antireversion agent would provide minimal impact to
optimally cured (t90) properties, and primarily react to
maintain crosslink density during conditions that initiate

C.
Table VI. Reversion data for various additives, 160
o

CV Formulation, 160 C
phr

MH
(dNm)

M 60
(dNm)

Reversion
(dNm)

phr

MH
(dNm)

M 60
(dNm)

Reversion
(dNm)

control

--

31.05

16.20

14.85

SR534
CIMB
PDM

2
2
2

27.57
29.60
36.03

23.70
26.20
24.40

3.87
3.40
11.63

5
5
5

30.60
32.99
48.58

33.25
32.89
36.80

0
0.10
11.78

phr

MH
(dNm)

M 60
(dNm)

Reversion
(dNm)

5
5
5

29.74
28.54
51.96

30.00
30.68
42.40

0
0
9.56

S-EV Formulation, 160oC


phr

MH
(dNm)

M 60
(dNm)

Reversion
(dNm)

control

--

29.61

21.20

8.41

SR534
CIMB
PDM

2
2
2

30.04
29.44
40.87

26.10
29.00
31.70

3.94
0.44
9.17

of the additives when cured to 60 minutes at 180C.


Again, both SR534 and CIMB virtually eliminated
reversion under these more demanding conditions,
while PDM allowed significant reductions in measured
torque over time.

The same compounds were evaluated at elevated cure


temperature as well. While extended cure time at
160C provides a comparison of additive performance
under overcure conditions, extending cure at 180C
can simulate reversion under high temperature service
conditions. Table VI outlines the reversion resistance

C.
Table VI. Reversion data for various additives, 160
CV Formulation, 180o C
phr

Reversion
(dNm)

control

--

14.30

SR534
CIMB
PDM

2
2
2

2.33
0
9.79

phr

S-EV Formulation, 180oC


Reversion
(dNm)

0
0
8.61

5
5
5

phr

Re version
(dNm)

control

--

12.24

SR534
CIMB
PDM

2
2
2

2.89
0
9.71

phr

Reversion
(dNm)

5
5
5

0
0
7.60

demonstrates the ability to provide adequate reversion


protection under high temperature conditions.

The cure behavior of the CIMB and SR534 at elevated


temperatures and 5 phr loading was characterized by
a marching modulus (Figure 6). Such behavior

60

Torque (dNm)

50
CIMB

40

SR534

30

PDM

20
control
10
0
0

10

20

30

40

50

60

Time (minutes)

C.
Figure 6. Activity of SR534 compared to CIMB and PDM; CV formulation, 5 phr additive, 180
Both SR534 and CIMB were included in an expanded
study to determine the optimal loading of anti-reversion
agents in the model CV formulation. Reversion was
determined for loadings between 0.5 and 5.0 phr of

SR534 or CIMB. The data is presented in Figure 7.


The reduction of reversion as a function of loading was
similar for each compound. In the given formulation,
reversion is effectively eliminated at 3 phr.

10

12

MH-M60 (dNm)

10
SR534

CIMB

6
4
2
0
0

phr

Figure 7. Optimization of additive loading in model formulation (CV).


Tensile Properties

were significantly higher than the control. The modulus


values of SR534 and CIMB were also elevated in this
model formulation. However, both SR534 and CIMB
displayed a significant improvement over PDM in terms
of modulus contribution during vulcanization. The
loadings of additive used in this study were selected to
provide data points both above and below that which
eliminated reversion (3 phr, Figure 7). It is suggested
that an optimized loading would typically be chosen
based on a balance between reversion resistance and
modulus increase. The optimal loading may be different
for each additive studied.

The physical properties of rubber compounds


employing SR534, CIMB, and PDM were compared
with each sample cured to the individually calculated
t90 cure times. Data was normalized to the control (no
anti-reversion agent) and is provided in the CV
formulation at both 2 and 5 phr (Figures 8 and 9,
respectively). The data highlights the departure from
the physical properties of the control formulation. It is
clear that PDM reacts preferentially during the initial
vulcanization step, as both 100% and 300% modulus

250

Normalized Value

200
control
150

SR534
CIMB

100

PDM
50
0
Tensile Elongation
Strength
%

100%
Modulus

300%
Modulus

Tear
Strength

Figure 8. Physical properties of compounds using 2 phr of additive, normalized to control (CV).

11

250

Normalized Value

200
control
150

SR534
CIMB

100

PDM
50
0
Tensile Elongation
Strength
%

100%
Modulus

300%
Modulus

Tear
Strength

Figure 9. Physical properties of compounds using 5 phr of additive, normalized to control (CV).
Test samples of the same compounds were intentionally
subjected to conditions that would lead to reversion.
Overcure conditions were simulated by curing past t90
times to 60 minutes. Following the methodology
outlined above, the data collected in the reverted state
was also normalized to the original control values (no

Deviation =

additive, cured to t90). In order to provide perspective


on how physical properties change as a function of
induced reversion, the deviation in normalized
properties is presented. Deviation is calculated
according to Equation 1:

property @ 60 minute cure

control property @ t90 cure

property @ t90 cure


control property @ t90 cure

Equation 1.
The data shows that compounds containing PDM lost
the most amount of modulus as a function of exposure
to reversion conditions, followed by the control.
SR534 and CIMB increased modulus. In both
formulations, SR534 had the least deviation in modulus,
while CIMB gained considerably. Perhaps most
importantly, the deviation in 300% modulus was the
least for SR534. Following the relative magnitude of
deviation in modulus is the loss of elongation and tear
properties.

By using this equation, the efficiency with which the


anti-reversion compounds maintain properties as a
function of heat history can be compared. The control
itself was also subjected to the same treatment, offering
a baseline for the relative amount of loss in properties.
Figures 10 and 11 present the results in the CV and
S-EV formulations at 5 phr additive. A negative
deviation represents a loss in properties with cure time.

12

100

Deviation

75
50

control

25

SR534

CIMB
PDM

-25
-50
-75
Tensile
Strength

Elongation
%

100%
Modulus

300%
Modulus

Tear
Strength

Figure 10. Deviation in physical properties as a function of induced reversion.


CV formulation, 5 phr additive.

100
75

Deviation

50
control

25

SR534

CIMB

-25

PDM

-50
-75
-100
Tensile Elongation
Strength
%

100%
Modulus

300%
Modulus

Tear
Strength

Figure 11. Deviation in physical properties as a function of induced reversion.


S-EV formulation, 5 phr additive.
both the CV and SE-V formulations in Figures 12 and
13, respectively. The net deviation from the optimally
cured properties is lowest for the multifunctional
acrylate ester product. SR534 was superior to CIMB
in maintaining physical properties when subjected to
overcure conditions.

By considering the overall deviation, the efficiency with


which each additive maintains physical properties can
be compared. Taking the sum of the deviations for
each compound (absolute values are used as any
departure from optimally cured properties would be
undesirable) the relative performance can be
compared. The data is presented in this manner for

13

CIMB
5 phr
2 phr
SR534

25

50

75

100

125

150

175

200

225

250

Ne t De viation

Figure 12. Net deviation in physical properties in the CV formulation.

CIMB
5 phr
2 phr
SR534

25

50

75

100

125

150

175

200

225

250

Ne t De viation

Figure 13. Net deviation in physical properties in the SE-V formulation.

Interestingly, net deviations increase at higher additive


loading (2 to 5 phr). These results are primarily driven
by the tendency of these compounds to increase
modulus when overcured. Again, optimization of

additive level balancing both modulus rise and


reversion resistance was not considered in this
fundamental study, and is best addressed in a specific
formulation.

14

versus the control. A lower tangent delta value can be


correlated to improved compound hysteresis. High
strain shear modulus (G, 1 Hz, 50% amplitude) data
is also provided. PDM increases G considerably
compared to the control, while SR534 and CIMB
produce values slightly below that of the control.
Overall, higher loadings of anti-reversion agent
produced increased G values. The addition of SR534
produces the lowest shear modulus. SR534 is the only
liquid product, and may contribute to lower compound
shear viscosity (cured).

Viscoelastic Properties
The viscoelastic properties of the CV compounds
were also compared. After curing to t90 in the MDR,
the samples remained in the test cavity and were
subjected to various strain amplitudes at a frequency
of 1 Hz and a temperature of 100C. Actual values
are provided in Appendix II. The normalized results
are given in Figure 14 for compounds containing 5 phr
additives. The addition of anti-reversion agents resulted
in decreased tangent delta (1 Hz, 10% amplitude)

160
140
Normalized Value

120
100
tan d

80

G'

60
40
20
0
control

SR534

CIMB

PDM

Figure 14. Viscoelastic properties of compounds using 5 phr of additive, normalized to control (CV).

60

Normalized Value

40
20
tan d

G'

-20
-40
-60
control

SR534

CIMB

PDM

Figure 15. Deviation in viscoelastic properties as a function of induced reversion. CV formulation, 5


phr additive.

15

crack width (mm)

Viscoelastic properties were subsequently evaluated


as a function of reversion. The samples were cured
for 60 minutes in the MDR and subjected to the strain
sweep described previously. These results are provided
in Figure 15 as a deviation from optimal properties
(normalized) according to the methodology outlined
previously. SR534 maintains the lowest tangent delta
values in the reverted state. The data suggests that not
only does SR534 maintain network integrity when
subjected to overcure conditions, but may also reduce
the heat build-up associated with applications
experiencing severe dynamic flex, reducing the autoacceleration quality of reversion associated with these
service conditions. Both the control and PDM
compounds lost considerable shear modulus upon
reversion (typically > 40%), while SR534 and CIMB
limited the reduction in G. The loss in viscoelastic

20
18
16
14
12
10
8
6
4
2
0

properties was generally reduced at higher additive


loading.
Flex Fatigue
SR534, CIMB, and PDM compounds were also
evaluated for flex fatigue resistance. The addition of
non-sulfur crosslinks or crosslinks of lower sulfur rank
will produce negative effects in dynamic cut growth
testing. To illustrate the trend, Figure 16 presents the
results using the control compounds. The control series
correlates cut growth with sulfur rank distribution. For
this series, 100% modulus values were similar. The
flex fatigue performance became progressively worse
as the concentration of mono- and di-sulfidic crosslinks
increased at the expense of polysulfidic. Crack growth
rate increases EV > S-EV > CV.

1.52
1.92
1.62

CV
S-EV
EV

50

100

150

200

250

cycles (E+03)

Figure 16. Flex fatigue results for CV, S-EV, and EV controls. 100% modulus values are indicated
(MPa).
Figure 17 outlines the results of fatigue testing when
incorporating the anti-reversion agents in the CV
compound (5 phr) and curing to t90. SR534 performed
equivalent to the CV control formulation, while CIMB
had a slightly elevated growth rate. The compound

using PDM showed highest cut growth. Interestingly,


the performance of SR534 was superior despite having
an initial modulus higher than the control, establishing
evidence that the inclusion of an anti-reversion agent
can provide benefits in dynamic flex fatigue resistance.

16

crack width (mm)

20
18
16
14
12
10
8
6
4
2
0

2.31

1.62
SR534

3.82

CIMB

2.69

PDM
control

50

100

150

200

250

cycles (E+03)

Figure 17. Flex fatigue results at 5 phr additive cured to t90. 100% modulus values are indicated
(MPa).

crack width (mm)

Test specimens of the same compounds were cured


to 60 minutes and tested. The results are provided in
Figure 18. In the reverted state, flex fatigue performance
now correlates with modulus. SR534 outperformed

20
18
16
14
12
10
8
6
4
2
0

CIMB, and these compounds increased modulus


compared to the results in Figure 17. The modulus of
the control and PDM was lower, the outcome of
reversion.

3.34
3.45

3.24
SR534
CIMB

1.24

PDM
control

50

100

150

200

250

cycles (E+03)

Figure 18. Flex fatigue results at 5 phr additive cured to 60 minutes. 100% modulus values are
indicated (MPa).
Anti-reversion agents SR534 and CIMB are not fully
reacted when the compounds are optimally cured, and
may help de-couple the dependence of modulus on
flex fatigue performance by improving the cured
network during testing. However, the vulcanizates that
were intentionally overcured prior to flexing would not

have this mechanism available. Therefore, modulus


would again strongly influence the results. Flex testing
from optimally cured samples may most accurately
reflect actual conditions. By interpreting the results
displayed in Figure 17 and 18, the benefits of including
anti-reversion agents can be realized.

17

Swelling Experiments

results are provided in Figure 19. The control loses


considerable network integrity with reversion. SR534
provides crosslink density values most similar to the
control at optimal cure, and maintains crosslink density
when subjected to overcure conditions. CIMB reacts
during vulcanization to increase crosslink density
prematurely, and loses considerable density as a
function of cure residence time. Swelling experiments
may best characterize the advantages possible when
incorporating SR534 into a reversion-prone
formulation.

Equilibrium swelling experiments are utilized to


determine the crosslink density (Vx) of vulcanizates.
An unfilled (no carbon black) version of the CV model
formulation was used to create compounds using both
SR534 and CIMB additives (5 phr). A control
compound was also included. Optimal cure times were
calculated using a rheometer, and samples cured to
both t90 and 60 minutes were prepared. Crosslink
densities were calculated for each vulcanizate. The

8.0E-05
7.0E-05

Vx (mol/cm )

6.0E-05
t90

5.0E-05

60 min
4.0E-05
3.0E-05
2.0E-05
1.0E-05
0.0E+00
control

SR534

CIMB

Figure 19. Crosslink density (Vx) of unfilled vulcanizates prepared at optimal cure times (t90) and 60
minutes.
behavior of this type of anti-reversion additive.
Compensation for the loss in performance necessitates
reformulation.

SUMMARY AND CONCLUSIONS


The ideal anti-reversion agent would provide reversion
resistance in a manner that does not significantly alter
the physical properties of the compound. Of the several
strategies that result in a network capable of maintaining
crosslink density under conditions that would normally
lead to reversion, only those additives which
compensate for the loss of network integrity at a similar
rate through the addition of new, heat-stable linkages
meet the above criteria. Alternately, products which
establish non-polysulfidic crosslinks during
vulcanization negatively affect desirable properties such
as dynamic flex fatigue and tear, and lead to higher
cured modulus. The activity of PDM characterizes the

SR534 is a multifunctional acrylate ester product that


contains no amine groups and has been developed to
minimize the effects on optimally cured properties and
provide maximum protection under conditions which
induce reversion. In the model formulation, SR534
demonstrated reversion resistance performance similar
to CIMB in overcure and high temperature conditions.
Both products reduced the impact on physical
properties and flex fatigue compared to PDM when
cured to t90. However, SR534 performed best
maintaining physical properties when subjected to

18

overcure conditions. Dynamic properties were also


improved using SR534. Swelling experiments showed
that crosslink density was maintained at elevated
temperatures using SR534 while both the control and
CIMB lost network integrity.

The data provided suggests that SR534 is capable of


forming additional, heat-stable crosslinks under
conditions that would normally result in reversion. By
eliminating reversion and best maintaining desirable
physical properties, SR534 is an effective amine-free
alternative to available anti-reversion products.

Appendix I. Physical property data.


CV FORMULATION
control

Cure time, minutes


Tensile Strength, MPa
Elongation, %
100% Modulus, MPa
300% Modulus, MPa
Tear Strength (Die C), kN/m
tan delta (1 Hz, 10%)
G' (1 Hz, 50%)
phr

SE-V FORMULATION

4.51
21.08
580
1.62
8.16
84.00
0.160
865.17

60.00
14.26
515
1.24
6.82
33.25
0.199
397.50

5.33
21.46
600
1.52
8.03
101.50

60.00
15.67
590
1.52
6.06
30.63

SR534

Cure time, minutes


Tensile Strength, MPa
Elongation, %
100% Modulus, MPa
300% Modulus, MPa
Tear Strength (Die C), kN/m

7.14
21.50
515
2.31
10.30
75.24

60.00
18.26
465
2.51
10.30
33.25

7.00
22.36
505
2.69
11.47
72.564

60.00
17.05
375
3.34
12.78
38.5

5.45
25.42
545
2.51
12.06
100.625

60.00
23.08
535
2.45
11.09
41.125

6.01
25.56
580
2.34
10.96
92.75

60.00
22.05
470
2.82
12.23
42.875

CIMB

Cure time, minutes


Tensile Strength, MPa
Elongation, %
100% Modulus, MPa
300% Modulus, MPa
Tear Strength (Die C), kN/m

6.07
24.39
635
2.07
8.89
85.75

60.00
21.46
460
3.07
12.61
38.50

6.50
24.84
645
2.31
8.96
92.75

60.00
20.74
430
3.45
13.44
49.88

5.57
24.39
630
2.03
9.44
118.13

60.00
23.80
480
2.93
13.06
49.88

5.86
24.94
640
2.24
9.37
97.13

60.00
21.98
435
3.45
14.02
44.63

PDM

Cure time, minutes


Tensile Strength, MPa
Elongation, %
100% Modulus, MPa
300% Modulus, MPa
Tear Strength (Die C), kN/m

6.11
23.12
490
2.89
12.33
64.75

60.00
17.29
490
2.10
8.89
48.13

6.35
22.87
450
3.82
14.47
49.00

60.00
19.19
435
3.24
12.30
41.13

6.26
25.05
480
3.45
14.71
70.88

60.00
22.01
500
2.51
11.44
42.88

7.15
25.05
435
4.62
17.16
63.00

60.00
21.36
450
3.41
13.26
46.38

Appendix II. Viscoelastic property data.


CV FORMULATION
control

Cure time, minutes


tan delta (1 Hz, 10%)
G' (1 Hz, 50%)
phr

4.51
0.160
865.17

60.00
0.199
397.50

SR534

Cure time, minutes


tan delta (1 Hz, 10%)
G' (1 Hz, 50%)

7.14
0.093
789.74

60.00
0.181
546.60

7.00
0.096
820.91

60.00
0.152
694.76

CIMB

Cure time, minutes


tan delta (1 Hz, 10%)
G' (1 Hz, 50%)

6.07
0.098
833.06

60.00
0.190
749.75

6.50
0.102
850.11

60.00
0.165
806.36

PDM

Cure time, minutes


tan delta (1 Hz, 10%)
G' (1 Hz, 50%)

6.11
0.091
958.04

60.00
0.193
513.47

6.35
0.096
1204.48

60.00
0.176
733.84

19

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12

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13

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14

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18
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19

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11

20

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21

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J. B. Class, US #6,245,861 (2001).

The information in this bulletin is believed to be accurate, but all recommendations are made without warranty since the conditions of use are beyond Cray Valley Company's
control. The listed properties are illustrative only, and not product specifications. Cray Valley Company disclaims any liability in connection with the use of the information,
and does not warrant against infringement by reason of the use of its products in combination with other material or in any process.

20