The Performance of Multifunctional Acrylates as Anti-Reversion Agents in Tire Applications

By Steven K. Henning Cray Valley USA, LLC Exton, Pennsylvania USA

Cray Valley USA, LLC Oaklands Corporate Center

468 Thomas Jones Way, Suite 100

Exton, PA 19341

Tel: 877-871-2729 Web: www.crayvalley.com

5066 01/10 1

ABSTRACT Multifunctional acrylates have found utility as effective anti-reversion agents in sulfur cured applications where overcure or high temperature cure conditions exist. In this paper, a new multifunctional acrylate product is evaluated in both conventional and semi-efficient vulcanization systems. Reversion resistance and cured physical properties of the resulting natural rubber/ carbon black vulcanizates are compared to other commercial products and efficient vulcanization systems. Multifunctional acrylates (Cray Valley SR534 and SR534D) provide excellent reversion resistance while providing a minimal impact on optimally cured properties. The object of the present study is to further explore the benefits of antireversion agents. Torque rheometry is used to predict the effect of these agents on preventing reversion in overcure or high-temperature cure conditions. Physical properties of optimally cured and overcured vulcanizates are provided, demonstrating the relative efficacy of anti-reversion agents. Further, flexural fatigue testing at elevated temperatures is used to differentiate the compounds with and without anti-reversion agents in simulated inservice conditions. It will be shown that, with the addition of anti-reversion agents, conventional and semi-efficient vulcanization systems can provide the reversion resistance properties of efficient vulcanization while maintaining the advantage in dynamic properties associated with these cure types. Finally, the mechanism of reversion prevention using SR534 is explored through fundamental swelling experiments and a model reaction system, with results differentiating it from an imidebased product.

INTRODUCTION As tires and other engineered rubber articles are designed to meet increasing process and service condition demands, inherent drawbacks of the sulfurderived network must be addressed. The bond strength of sulfur linkages determine the unique performance attributes of the system, but also account for service limitations. A network derived from polysulfidic linkages is preferred for components subject to dynamic strain where improved flexural fatigue and tear properties are desired. Having lower bond dissociation energies,1,2 polysulfidic linkages break more readily under strain, but due to their chemical nature also possess the ability to reform and alleviate stresses.3,4 The major disadvantage of polysulfidic networks is poor thermal stability. Thermal stress on the vulcanizate can lead to a degradation process known as reversion. In sulfur cured vulcanizates, reversion can be defined by a reduction in physical properties associated with a loss 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 which results in weaker network structures.5,6 The result is a decline in physical properties and a decrease in the performance of the rubber article.7 Reversion can take place both during (in process) and after (in service) the initial vulcanization event. A desire for improved manufacturing efficiency may lead to increased curing temperatures which can cause higher rates of reversion. A move toward high performance and ultra high performance tire design places increased demands on tire components, including loads and deflections which can lead to higher running temperatures. Many run-flat designs utilize inserts which bear the load of the vehicle under zero-inflation conditions. Heat build-up in these scenarios can lead to in-service reversion and a loss in physical properties of the critical internal components. Durability of the rubber article can be negatively affected.

Anti-reversion agents are often used to mediate the effects of the reversion process. The most effective approach is to compensate for the destruction of crosslinks by adding chemical additives that react to form new crosslinks when reversion processes are initiated. Ideally, the processes have similar rates such that crosslink density is maintained. Both multifunctional acrylate esters and imide-based antireversion agents have been shown to effectively combat reversion induced in laboratory conditions.8,9 Previous work compared a proprietary multifunctional acrylate ester product (Cray Valley SR534) to 1,3bis(citraconimidomethyl)benzene (CIMB).10 Both products effectively prevented reversion in a model carbon black filled cis-poly(isoprene) compound. In addition, SR534 minimized the effects on optimally cured properties (t90) and provided protection under conditions which induce reversion. Tensile, shear, and dynamic properties were compared. The data provided suggests that SR534 is capable of forming additional, heat-stable crosslinks preferentially during overcure conditions which would typically result in reversion. The object of the present study is to further explore the benefits of antireversion agents. SR534 and CIMB are added to conventional and semi-efficient vulcanization systems and compared to an efficient cure system. Torque rheometry is used to predict the effect of these agents on preventing reversion in overcure or high-temperature cure conditions. Physical properties of optimally cured and overcured vulcanizates are provided, demonstrating the relative efficacy of antireversion agents. Further, flexural fatigue testing at elevated temperatures is used to differentiate the compounds with and without anti-reversion agents in simulated in-service conditions. It will be shown that, with the addition of anti-reversion agents, conventional and semi-efficient vulcanization systems can provide the reversion resistance properties of efficient vulcanization while maintaining the advantage in dynamic properties associated with these cure types. Finally, the mechanism of reversion prevention using SR534 is explored through fundamental swelling experiments and a model reaction system, with results differentiating it from the imide-based product.

EXPERIMENTAL Rubber Compounding A model compound formulation was designed for its predilection for reversion.10 The formulation, given in Table I, is based on cis-poly(isoprene) (natural rubber), as it has the highest allylic hydrogen concentration of the diene-based elastomers. The curative loadings for conventional (CV), semi-efficient (S-EV), and efficient (EV) vulcanizations are provided. These are model formulations that have not been optimized for a specific application. Table I. Model formulations.
Ingredient, phr Non-Productive Natural Rubber (CV-60) Carbon Black (N 330) Zinc Oxide Stearic Acid Productive Antioxidanta Anti-Reversion Agent Sulfur TBBS
b

CV

S-EV

EV

100.0 50.0 5.0 1.5 1.0 2.5 0.6

100.0 50.0 5.0 1.5 1.0 1.2 1.6

100.0 50.0 5.0 1.5 1.0 0.2 2.0 2.0

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

TMTDc
a

2,2,4-trimethyl-1,2-hydroquinoline N-t-butylbenzothiazole-2-sulfenamide

b c

tetramethylthiuram disulfide

Using an internal mixer, a non-productive masterbatch was prepared containing all ingredients except antireversion agents and curatives. The productive stage was mixed using a two-roll mill. Milling times were approximately 7 minutes. Productive stock was aged overnight prior to testing. Physical Testing The determination of vulcanization behavior was performed on a Tech Pro MDPT moving die rheometer (MDR) according to ASTM D 5289 at both 160C and 180C. The individual calculated t90 values (time to 90% of maximum torque, optimal cure) were used for subsequent test sample preparation (compression molded). In addition, reverted samples were prepared by curing to 60 minutes (overcure). Stress-strain and tear data was acquired on a Thwing-Albert Materials Tester following ASTM D 412 and D 624-C. DeMattia flex fatigue was determined according to ASTM D

813 under conditions starting at room temperature and also at an elevated constant temperature of 100C. Swelling Experiments Samples were mixed in a Brabender Prep Mixer using the same formulation in Table I 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 from which 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 Rhener11 and modified with equivalent terms derived from theories of rubber elasticity. The c parameter used for the toluene/cispoly(isoprene) system was 0.37.

RESULTS and DISCUSSION Torque Rheometry Originating from weaker polysulfidic crosslinks, reversion can be minimized using efficient vulcanization systems which promote the formation of stable monoand disulfidic linkages. However, this strategy has a disadvantage in that tear properties and dynamic performance (flexural fatigue) can be adversely affected. Strong crosslinks possess high dissociation energies and resist rupture 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.1,2 The labile nature of the polysulfidic crosslinks contribute to both improved dynamic properties,3 but also causes reversion. The rheometer cure profiles for the control formulations are provided in Figure 1 (no anti-reversion agent added) measured at 160C. It is clear that as the sulfurto-accelerator ratio decreases reversion was reduced. In the EV case, sulfur donors are utilized and no reversion was evident.

35 30 25
Torque (dNm)

EV S-EV CV

20 15 10 5 0 0 15 30 45

60

75

Tim e (min utes)

Figure 1. Cure profiles of conventional (CV), semi-efficient (SE-V) and efficient (EV) vulcanizations; 160C. The performance of the anti-reversion agents in the reversion-prone CV and S-EV formulations is summarized in Figures 2 and 3, respectively, again at 160C. SR534 and CIMB are added at 2 phr in both compounds, with the EV compound (no reversion agent) included for comparison.

CV Formulation 35 30
Tor que (dNm)

25 20 15 10 5 0 0 15 30 45 60

EV control CIMB SR534 CV control

75

Time (mi nutes)

Figure 2. Activity of anti-reversion agents in CV formulation; 2 phr, 160C. Both SR534 and CIMB effectively reduce reversion in the CV formulation at this loading. After an apparent induction period, CIMB tends to produce a marching modulus while SR534 plateaus to a constant torque value. In the S-EV formulation, both anti-reversion agents closely follow the rheometer profile of the EV cure and more effectively compensate for desulfuration.

S-EV Formulation
35 30 Torque ( dNm) 25 20 15 10 5 0 0 15 30 45 60 75 Tim e (mi nutes)

CIMB EV control S R534 S -EV control

Figure 3. Activity of anti-reversion agents in S-EV formulation; 2 phr, 160C. These agents were also evaluated in the S-EV formulation at an elevated cure temperature of 180C in an attempt to simulate accelerated high temperature service conditions or model the results of a high temperature cure cycle. Figure 4 shows that while both agents reduced reversion, SR534 more closely matches the eventual torque value (60 minutes) of the EV system, while at this loading CIMB suffers from marching modulus. Again, an induction period is seen before apparent crosslink density is increased subsequent to the initial maximum torque value (MH). It should be noted that loading of the anti-reversion agents has not been optimized.

S-EV Formulation
35 30
Torque (dNm)

CIMB SR534 EV control S-EV control

25 20 15 10 5 0 0 15 30 45

60

75

Tim e (mi nutes)

Figure 4. Activity of anti-reversion agents in S-EV formulation; 2 phr, 180C. Physical Properties Anti-reversion agents are often used in applications where cured rubber components are subjected to extreme in-service conditions. Elevated temperatures, whether generated internally by hysteretic heating or by high ambient conditions, accompanied by large deformations may induce reversion. Testing the physical properties of vulcanizates cured both to the t90 of the compound and after a substantial overcure (60 minutes) may provide insight to the utility of antireversion additives. Tensile and tear properties. The physical properties of the model S-EV compounds employing 2 phr of anti-reversion agents were compared to the control S-EV compound after being cured to both t90 (approximately 4 minutes in each case) and 60 minutes of cure time (160C). The properties of the EV compound have also been included for reference. Table II provides the data.

Table II. Physical properties of vulcanizates cured to optimal times and overcured to 60 minutes (reverted).
original SR534 CIMB S-EV S-EV 4 4 21.79 22.90 523 552 2.60 2.54 11.18 10.74 83.0 79.6 reverted SR534 CIMB S-EV S-EV 60 60 20.77 21.23 510 475 2.80 3.03 10.67 11.84 61.3 58.6

Anti-reversion Agent (2 phr) Cure System Cure Time (minutes) Tensile Strength (MPa) Elongation (%) 100% Modulus (MPa) 300% Modulus (MPa) Tear Strength (Die C) (kN/m)

none S-EV 4 23.92 550 2.59 11.39 109.6

none EV 4 17.90 481 2.36 9.10 50.8

none S-EV 60 19.37 505 2.28 9.71 42.4

none EV 60 12.79 368 2.44 13.33 43.4

The S-EV control displayed the largest net change in physical properties. The addition of anti-reversion agents compensated for this loss and more effectively maintained properties. Note that the original tear strength of the S-EV compounds was significantly better than the EV compound. The anti-reversion

compounds, when subject to overcure and an overall reduction in tear strength, maintained values at least equivalent to the original EV compound tear. The EV compound produced the least change in tear with overcure.

Figure 5 presents a comparison of the normalized deviation in properties and provides a visual measure of the overall change in physicals with reversion. Equation 1 was used to calculate the deviation in physical properties as a function of reversion. Deviation = [property(60 min.) property(t90)] Equation 1. Deviation calculation. The results for each physical property tested were normalized to the deviation in the control (set at -100, as each property of the control was reduced with
300
Normalized Dev iation

overcure). Any departure from zero net change would be considered detrimental upon compound ageing, but it can be seen that the compound containing SR534 demonstrates the least amount of deviation from optimally cured physicals after the overcure event. The performance of SR534 is partly driven by maintaining crosslink density at this loading, rather than a loss in crosslink density (control) or marching modulus (CIMB) (Figure 3). Similar improvements in performance when using multifunctional acrylates was reported by other investigators, including dynamic shear measurements.8

200 100 0 -100 -200 -300

Ten sil e Stre ng th % El ong atio n 100 % Modu lus 3 00% Mo dul us Te ar S tre ngt h

S-EV co ntrol SR534 CIM B EV cont rol

Figure 5. Normalized comparison of the deviation in physical properties as a function of overcure (reversion); S-EV formulation, 2 phr anti-reversion agent. Flexural fatigue properties. DeMattia flexural fatigue testing was performed under both conditions starting at room temperature and at an elevated constant temperature of 100C. The latter conditions were investigated as an attempt to test the efficacy of antireversion agents under severe in-service conditions. The most notable difference is that the DeMattia testing was performed under aerobic conditions which may not be the case for in-service reversion of internal tire components, for example. However, the testing does offer a direct comparison between the agents and the control formulations. The benefits of polysulfidic crosslinks in the vulcanizate are illustrated in Figure 6 which compares the controls (no anti-reversion agent) of the various vulcanization systems and provides results when 2 phr anti-reversion agents are included. The 100% modulus values were similar (approximately 2.0 MPa). As reported in earlier studies,14 improvements in flexural fatigue properties can be correlated to the polysulfidic crosslink content of the vulcanized network. The flex fatigue resistance of the controls improves EV < S-EV < CV. The addition of anti-reversion agents in the formulation does not reduce the flex fatigue. In the CV formulation, SR534 improves the crack growth resistance. The ability of anti-reversion agents to improve upon heatbuild up and durability under high temperature testing conditions when tested on a compression flexometer (Goodrich) has previously been demonstrated.15

14.0 12.0
Crac k Widt h (mm)

EV control

S -EV control CIMB S R534

CV control CIMB

10.0 8.0 6.0 4.0 2.0 0.0 0 50000

SR534

100000 Cycles

150000

200000

250000

Figure 6. DeMattia flex fatigue results performed under ambient (room temperature) conditions. Equilibrium swelling experiments. 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 produced compounds including either SR534 or CIMB additives (5 phr). A control compound was also included. Samples cured to both t90 (4 minutes) and 60 minutes were prepared. Crosslink densities were then calculated for each vulcanizate based on the swelling experiment. The results are provided in Figure 7. 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 appeared to partially react during vulcanization and increased crosslink density prematurely. CIMB also lost density as a function of mold residence time. Swelling experiments may most clearly characterize the potential advantage of incorporating SR534 into a reversion-prone formulation.

8.0E-05 7.0E-05 6.0E-05 Vx (mo l/cm) 5.0E-05 4.0E-05 3.0E-05 2.0E-05 1.0E-05 0.0E+00 control SR534 CIMB
3

4 minute cure 60 minute cure

Figure 7. Crosslink density (Vx) of unfilled vulcanizates prepared at optimal cure times (t90) and 60 minutes.

These results, in conjunction with the rheometer, tear, and flexural fatigue data in the previous sections, demonstrate that the inherent compromise between improved dynamic physical properties and reversion in CV and S-EV cure systems may be corrected through the use of anti-reversion agents. This is possible with minimal reformulating due to the documented crosslink-compensating activity of SR534. Mechanistic Study The anti-reversion agents compared in this study are based on different reactive groups. It is therefore possible that the reaction mechanisms through which each form new crosslinks may also be different. Crosslinking through Diels-Alder reactions involving the methyl-substituted imide groups of CIMB has been documented.9 The mechanism is initiated by 1,4elimination reactions during desulfuration which produces conjugated unsaturation in the polymer chain. Crosslinks are formed through Diels-Alder reactions

between the conjugation and imide structures, resulting in load-bearing crosslinks formed through the difunctional CIMB. However, the ability of CIMB and SR534 to participate in other reactions, including ene and radical addition has also been postulated.8 A basic study was devised in an attempt to elucidate the relative activity of SR534 and CIMB in the model compound system. To the non-productive masterbatch of the formulation provided in Table II, 5 phr SR534 or CIMB was added; no curatives (sulfur, accelerators) were included. The MDR was employed to measure any evolution of torque as a function of anti-reversion agent loading and temperature. Compounds were tested between 100C and 200C for 60 minutes. The increase in torque is taken as a measure of crosslink density. The control (no anti-reversion agents) produced a torque rise of 0.21 points when tested at 160C. Figures 8 and 9 provide cure as a function of temperature for CIMB and SR534, respectively.

CIMB, 5 phr 10 9 8 7 6 5 4 3 2 1 0 0 10 20 30 40 50 60
Ti me (m inu tes)

To rque ( dNm)

200C 180C 160C 100C 70

Figure 8. MDR torque profiles for CIMB as a function of testing temperature; no curatives, 5 phr CIMB. As expected, CIMB demonstrated little evidence of reaction, consistent with the previously reported mechanism. The absence of initial polysulfidic crosslinks precludes the formation of conjugated unsaturation, rendering the Diels-Alder reaction pathway unavailable.

SR534, 5 phr 10 9 8 7 6 5 4 3 2 1 0 0 10 20 30 40 50 60
Tim e (m in ute s)

200C 180C 100C 160C

Torque (dNm)

70

Figure 9. MDR torque profiles for SR534 as a function of testing temperature; no curatives, 5 phr SR534. Only SR534 built appreciable torque at elevated temperatures, and showed some baseline activity at temperatures below 160C. This data does not eliminate a Diels-Alder reaction pathway but suggests that another mechanism may be available to SR534. As both compounds are susceptible to radical addition reactions, the differentiation in activity would suggest an alternate pathway. The ene reaction, requiring only a reactive enophile (acrylate ester) and allylic hydrogen, could be a possibility. It is possible that the steric hindrance involving the methyl substituent of the imide effectively excludes an ene reaction for CIMB at lower temperatures. The ene reaction has also been documented having a higher activation energy than Diels-Alder reactions.1 So it would be conceivable that SR534, capable of reaction through both mechanisms, can offer crosslink-compensating activity at lower temperatures or under conditions where conjugated unsaturation is not available. While the results of this study are not definitive, they do suggest a difference in the potential activity of the two anti-reversion agents as a direct result of their structure. It is possible, through a potential ene reaction pathway, that SR534 may offer expanded application utility. SUMMARY and CONCLUSIONS Sulfur cure systems can be differentiated by the relative amounts of polysulfidic crosslinks they form. Networks of high polysulfidic linkage concentration improve tear and dynamic properties and extend flexural fatigue life. Heat sensitivity, which is manifested as network reversion, is an issue when employing CV or S-EV systems. The EV system eliminates reversion in the cured compound, but displays poorer physical properties. Antireversion agents which compensate for the loss of polysulfidic crosslink density by forming new, stable crosslinks can better maintain physical properties of compounds subject to overcure or high temperature in-service conditions. With the inclusion of SR534 in a CV or S-EV formulation, initial tensile and dynamic properties are similar for compounds cured under optimal conditions and largely maintained as a function of reversion. Tear strength and flexural fatigue performance are improved versus EV cured compounds after subject to high temperature or overcure conditions. SR534 therefore provides a favorable alternative to using EV cure systems as an anti-reversion strategy.

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REFERENCES
L. H. Palys and P. A. Callais, Rubber World 229(3), 35 (2003). 2 P. R. Dluzneski, Rubber Chem. Technol. 74, 451 (2001). 3 A. G. Thomas, J. Polym. Sci. 31, 467 (1958). 4 L. Bateman, ed., The Chemistry and Physics of RubberLike Substances, MacLaren, London, 1963. 5 M. Mori, Rubber Chem. Technol. 76, 1259 (2003). 6 C. H. Chen, J. L. Koenig, J. R. Shelton, and E. A Collins, Rubber Chem. Technol. 54, 734 (1981). 7 U. Shankar, Rubber Chem. Technol. 25, 241 (1952). 8 E. J. Blok, M. L. Kralevich and J. E. Varner, Rubber Chem. Technol. 73, 114 (2000).
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A. H. M. Schotman, P. J. C. van Haeren, A. J. M. Weber, F. G. H van Wijk, J. W. Hofstraat, A. G. Talma, A. Steenbergen, and R. N. Datta, Rubber Chem. Technol. 69, 727 (1996). 10 S. Henning and S. Shapot, Paper 13, Fall Technical Meeting, Rubber Division, ACS, Pittsburgh, PA, November 1-3, 2005. 11 P. J. Flory and J. J. Rhener, J. Chem. Phys. 11, 521 (1943). 12 W. Cooper, J. Polym. Sci. 28, 195 (1958). 13 L. Bateman, ed., The Chemistry and Physics of RubberLike Substances, MacLaren, London, 1963. 14 W. L. Cox and C. R. Parks, Rubber Chem. Technol. 39, 785 (1966). 15 R. N. Datta and M. S. Ivany, Rubber World 212(5), 24 (1995). 16 B. B. Snider, Acc. Chem. Res. 13, 426 (1980).
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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.

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