A NEW CARBON BLACK-RUBBER COUPLING AGENT TO IMPROVE WET GRIP AND ROLLING RESISTANCE OF TIRES L. GonzA.ez, A. Ropricurz, J. L. De BENITO, AND A, MARCOS: Instituto pe Ciencia ¥ TecNowodta De PoLIMEROS. C.S.1.C., JUAN DELA CiERVA, 8, 28008 MaDaip, SPAIN ABSTRACT ‘The compound p-aminobenzenesulfonyl azide was developed as a new type of carbon black to rubber coupling agent. Its addition to rubber compounds increases resilience and moduli while reducing abrasion loss. The behavior of this coupling agent is confirmed by the dynamic mechanical response of the vuleanizates—the rubber T, is shifted to higher temperatures. Rubber compositions containing this coupling agent may be used in tire treads to reduce rolling resistance and improve wet skid resistance. These attributes were estimated from dynamic property measurements, INTRODUCTION Advances in automotive engineering inevitably result in new requirements for tires. In addition, recent legislation for traffic safety, fuel consumption and air pollution is a decisive factor for future research and developments. The tire industry will thus be forced to continue its R&D at a significant level of cost and hence remain an industry with a high innovation component. In this context, the main proposals for innovation point in three directions: new concepts in tire design; improvements of existing tire materials through the development of new polymers'*; and, last but not least, the incorporation of “chemical promotors” or “coupling agents” into the elastomer /carbon black masterbatch to enhance the degree of filler-polymer interaction.‘ This paper is aimed at innovations in this latter area. In general, the characteristic improvements observed in vulcanizates prepared with cou- pling agents are: decreases in hysteresis; increases in tensile modulus and electrical resistivity; reduction in hardness; better abrasion resistance; and little or no change in ultimate tensile strength and elongation. With these improvement opportunities in mind, the paper examines a new coupling agent designed to increase the density and strength of elastomer/carbon black interactions, Quite a few chemical compounds can act as coupling agents: N-( 2-methyl-2-nitropropy!)- 4-nitrosoaniline; N,4-dinitroso-N-methylaniline; p -nitrosodiphenylamine; p-nitroso-N,N-di- methylaniline; ete.°* Among these compounds, the nitroso derivatives proved to yield the best results, yet were withdrawn from use due to their suspected carcinogenic effects. As a consequence, other coupling agents were tested, such as hydroxy quinoline derivatives, nitro compounds containing a sulphur atom, ete, None of these, however, equaled the relevance and benefits of the nitroso derivatives. Recently, it has been found that the benzofuroxan added during the mixing of the masterbatch promotes increased bonding between the elastomer and carbon black, according to Graves.® Eventually, and in light of the above mentioned arguments, the coupling properties of aryl sulphonyl azide derivatives were examined in a rubber /earbon black environment. ‘Thanks to advanced analytical techniques, carbon black is known to possess molecular surface groups containing carboxylic acid, phenols, quinones, carboxylic lactone, ete.!™!? This is why p-aminobenzenesulfonyl azide (Amine-BSA) was chosen as the coupling agent. In principle, the azide function reacts with the rubber, whereas the amine function reacts with the acidic carbon black surface. Thus high energy bonds are achieved between the polymer and the filler particles. 266CB-RUBBER COUPLING AGENT 267 EXPERIMENTAL MATERIALS ‘The elastomer used in this research was styrene-butadiene copolymer rubber (SBR) manufactured by Bayer under the trade name Krylene 1502. The styrene content is 23.5 wt %. The monomers are randomly arranged in the chain in this emulsion-polymerized rubber type. The carbon black, Calblack N330, was supplied by Repsol, Spain. The 4-acetamido- benzenesulfonyl chloride was a Fluka product and the sodium azide was supplied by Panreac. ANALYTK METHODS ‘The infrared spectra were obtained on KBr pellets using a Perkin-Elmer Model 457 IR Spectrometer. The "H and "°C nuclear magnetic resonance spectra were obtained in DMSO- don a 200 MHz Bruker Spectrometer. BLENDING AND CURING A masterbatch —consisting of rubber, carbon black, zinc oxide and stearic acid—was compounded on a two-roll mill. Then the Amine-BSA was added to the mix using a Brabender and was heat-treated at 160°C and 60 rpm for 5 minutes. The accelerant and the sulphur were added at a temperature of 40-50°C on an open mill. The heat treatment caused the Amine-BSA to decompose, giving rise to the filler~polymer crosslinking reaction. This heat treatment was applied to the control blend under the same conditions, Measurements of the degree of cure were conducted in a Monsanto Moving Die Rheometer, Model MDR 2000 E. All samples were subsequently cured to their respective optimum times (£97 on the rheogram) PHYSICAL TESTING Tensile tests were performed on an Instron Tensile Tester with a grip separation speed of 50 em/min. The tests were carried out at room temperature. The test samples were cut from the vulcanized materials with a microtensile dumbell-type die. All tensile results re- ported in the tables are the average values of five tests. Tensile, tear and hardness tests were conducted following ISO standards and abrasion resistance was determined according to DIN 52516. DETERMINATION OF THE CR INK DENSITY ‘The volume fraction in the swollen network, V,, in the vulcanizates was determined by means of equilibrium swelling in toluene at 30°C. Test samples were placed in reagent-grade toluene in test tubes and allowed to reach equilibrium swelling at room temperature (<3 days). The samples were immediately weighed on an analytical balance to nearest 10~° g, then dried in a vacuum oven for 24 h at 60°C to remove all solvent, and reweighted. In this research the V, values were used to represent the crosslink density of the cure compounds. DYNAMIC MECHANICAL MEASUREMENTS. Viscoelastic dynamic measurements were conducted on a strip cut from the network sheets, using a Metravib Viscoelasticimeter, Model Mark 03, at a frequency of 15 Hz. The samples (dim. 30 X 3 X 2 mm) were heated, not in the continuous mode, but stepwise, covering a range from —80 to +70°C. Before making any measurements, the samples were held at the chosen temperature for five minutes. PREPARATION OF P-AMINOBENZENESULFONYL AZIDE 24.32 g 4-acetamidobenzenesulfonyl chloride dissolved in 250 mL acetone were filled into a 500 mL-reactor. The solution is ice-chilled to a temperature of 5°C. A solution of 75 mL268 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 69 wae Scueme 1 distilled water and 7.43 g (0.114 mol) sodium azide was added dropwise with stirring, taking care that the temperature in the reactor remained below 5°C. The solution was stirred for ‘90 minutes and then poured on ground ice. The resulting precipitate was filtered and washed several times with distilled water. The sulfonyl azide derivative was recrystallized from an acetone-water solution and vacuum-dried to constant weight, yielding 22.74 g p-acetami- dobenzenesulfonyl azide (94% yield). This azide was stored in dessicator. For hydrolysis of this product, the method described by Cremlyn'® was followed: In a 200 mL. reactor containing 4 g (0.017 mol) of 4-acetamidobenzenesulfonyl azide, 25 mL. concentrated hydrochloric acid were added. The solution was refluxed with stirring for 1 h. Upon cooling, the product was neutralized with a saturated sodium bicarbonate solution until a pH of 6-6.5 was reached. The whitish-brown precipitate was filtered and rinsed in water and finally vacuum-dried without heating. The yield amounted to 3.28 g p-amino- benzenesulfonyl azide (82% yield). Element analysis gave the following results: Caled. for CyHgN,0,8: C, 36.36%; H, 3.03%; N, 28.28%; S, 16.16%, Found: C, 36.19%; H, 3.14%; N, 28.03%; S, 16.35%. Spectral analysis of product.—(see Scheme 1) The IR spectrum (KBr pellet) was analyzed as follows: 3410 cm”, asymmetric N-H stretching; 3350 cm™, asymmetric N-H stretching; 2080 cm, asymmetric -N; stretching; 1578 em”, N-H in-plane bending; 655 cm”, N-H out-of-plane bending; 1170-1165 cm", symmetric SO,-N and -N; stretching; 830 em", C- H aromatic out-of-plane bending. NMR analysis (DMSO-d,) yielded the following: 'H NMR: 6 = 7.59 (~CH=C(SO.Ns)-CH-); 6 = 6.71 (-CH=C( NH) )-CH); 6 = 6.54 (-NHp). "°C NMR: 6 = 120.76 (C, carbon); 5 = 129.97 (C; carbon); § = 113.04 (Cs carbon); § = 155.31 (C, carbon). (The subscripts refer to the formula in Scheme 1.) ‘These analysis and spectral results are consistent with the formula given in Scheme 1 RESULTS AND DISCUSSION POSSIBLE MECHANISM OF COUPLING REACTION BY P-AMINOBENZENESULFONYL AZIDE, ‘The organic azide decomposes thermally at about 155°C generating a nitrene group capable of extracting one hydrogen and becoming linked to the polymer. A possible reaction mech- anism is shown in Scheme 2 During the process of Brabender mastication process at 160°C, the azide decomposes generating nitrene reagent species which react with the polymer and bond to it. Our laboratory est a soe “a {soi +t Octo heat ta CHSC + He Som ayCB-RUBBER COUPLING AGENT 269 ye se 80y covalent coupling one oO carton ack pee 1 Ionic coupling ScHeMe 3 is experienced in these reagents as a result of research in rubber crosslinking with bi-func- tional sulphonyl azides." In addition, the dangling amine function —by means of abstrac- tion of one hydrogen atom—is capable of an ionic bond forming reaction with the carboxylic acids groups present on the carbon black surface, or even forming a covalent bond through the generation of an amide group. These alternatives are illustrated in Scheme 3. Another possibility is the formation of hydrogen bridges between the amine group and lactone, phenol, ete. functions, all present on the filler surface. BEHAVIOR OF AMINE-BSA AS A COUPLING AGENT The typical tire formulations, shown in Table I, include a control compound and the experimental compound containing the coupling agent Amine-BSA. The table also gives the rheometer-determined curing parameters at 160°C for both compounds. ‘The physical properties of the two vulcanizates are shown in Table II. Amine-BSA in- corporation gives rise to a significant increase in the 100% modulus, abrasion resistance and ‘TapLEL Recipes AND PROPERTIES OF UNVUI Compound Control Amine-BSA Polymer SBR-1502 100 100 Carbon black (N330) 45, 45 Zine oxide 5.0 5.0 Stearie acid 2.0 20 Amine-BSA. = 0.37 cBs* 2.0 20 Sulphur 20 2.0 Monsanto Rheometer at 160° 190, min 45 45 10.0 9.0 47.0 475 3.0 3.0 benzothiazole sulphenamide.270 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 69 ‘Tame I PHYSICAL PropERries OF SBR VULCANIZATES Compounds Control _Amine-BSA Tensile strength, MPa 20.30 21.30 Elongation, % 275 270 100% Modulus, MPa 4.95 7.16 ‘Tear strength, die delft, N 33.6 30.4 Hardness, Shore A 69 68 Rebound resilence, % 44 47 Abrasion loss, mm* 69 58 Volume fraction of rubber in the swollen network, V, Glass transition temperature, T,, °C rebound resilience; ultimate tensile strength and elongation remain practically unaffected by the additive. The crosslink density of the vuleanizates is indicated by their equilibrium swelling value, V,. As shown in Table II, the compound containing Amine-BSA has a higher V, value than the control sample, and hence possesses a greater crosslink density than the control com- pound. This finding is further confirmed by the values of the glass transition temperature, T,, of the two compounds, as shown in Figure 1. The higher glass transition temperature of the sample containing Amine-BSA is conclusive evidence for the presence of a network with a greater number of filler-polymer interactions, constraining molecular mobility in the poly- mer and hence causing the polymer 7, to rise.) 08 tend 03 or -60-20 20 60 Tee) Fic. 1. —Loss tangent vs. temperature for SBR compounds; (O) control; (C) with Amine-ESA coupling agent.CB-RUBBER COUPLING AGENT am ‘Tapue IIL Loss TANGENT OF SBR VULCANIZATES Temperature, * Control __Amine-BSA -15 0.875 0.425 +60 0.135 0.105 ‘Tame IV ‘Wer Grip AND ROLLING REsIsTENCE OF SBR ‘VULCANIZATES Relative wet Relative rolling grip resistance resistance ‘Compound ) e Control 100 100 Amine-BSA 113 78 ESTIMATES OF ROLLING AND WET GRIP RESISTANCE ‘Two important requirements for tire treads are: (i) reduced rolling resistance (fuel con- sumption) and (ii) improved wet skid resistance (safety). However, this must occur without any loss in overall performance characteristics. In this research, the dynamic properties were chosen as the method to estimate rolling resistance and wet grip resistance of the vulcanizates. Saito" and Fujimaki, ® using a vis- coelastic model, have shown that rolling and wet skid performance show a good correlation with tan 6 values at the different temperatures ranges. It is also known that wet skid resistance can be improved by increasing the value of loss tangent at the -15°C at a test frequency of 15 Hz. In the same manner, the rolling resistance can be lowered by reduction of tané at 60°C. Table III shows the loss tangent data at -15°C and 60°C at frequency of 15 Hz. From this data, it can be observed that both responses are suited to improved behavior: increased Joss tangent at low temperature and reduced loss tangent at the higher temperature range. Table IV shows the results in terms of improvement percentages with the values of the control sample serving as a reference. Rolling resistance is shown to diminish 22%, while the respective improvement increment in wet grip is 13%. CONCLUSION Amine-BSA behaves like a black /rubber coupling agent.'* Its incorporation into a rubber composite increases rebound resilience and the moduli at low strain, and reduces abrasion oss, while hardness, tensile strength and elongation at break remain essentially unaltered. ‘The coupling behavior of the coupling agent is confirmed by the dynamic mechanical response of the vulcanizates. The shift of the rubber 7, to higher temperatures in the Amine-BSA compound is evidence for a respectively greater number of filler-polymer interactions. Yet the character and effect of the Amine-BSA coupling agent comes to light in the loss tangent data at the critical temperatures and frequencies for rolling resistance and wet grip assess- ment of a tire. The results reported will have to be complemented by other measurements, such as heat, build-up, bound rubber, carbon black dispersion in the rubber (by means of electric con- ductivity measurements on the vuleanizates), and other properties.272 RUBBER CHEMISTRY AND TECHNOLOGY In principle and in the light of the results obtained, this new coupling agent for carbon black-rubber crosslinking may be expected to become a strong candidate for industrial ap- plications sine —apart from the benefits reported —it does not present the potential toxicity concerns associated with the other known coupling agents, as stated in the introduction to this paper. ACKNOWLEDGEMENT The authors wish to thank the CICYT, MAT-092/0917, for partial financial support. REFERENCES *K.H, Nordisiek, Proc. 94% Meeting Int. Rubber Study Group, June 1981, London. *K.H, Nordsiek, Paper no. 48, presented at a meeting of the Rubber Division, American Chemical Society, May 8-11, 1084, Indianapolis; abstract in Ruane Cuz. Tecunot. 68, 201 (1985). ° J, Walker and 8, E. Horne, Blastomerics, 117(8), 22 (1985). “7. Yamaguchi, I. Kurimoto, H. Nagasaki, and T. Okita, Rubber World, 199(5), 30 (1988). ©-7, Yamaguehi, I. Kurlmoto, H. Nagasaki, and T.Okita, Kautsch. Gummi Kunstst. 42, 403 (1989). © A.R. Payne, P. M. Swift, and M. A. Wheelans, J. Rubber Res. Inst. Malaya 22, 275 (1969). 7 HM. Leeper, C. L. Gable, J. J. D'Amico, and C. C. Tung, Rubber World 136, 413 (1956). © A.S. Lykin, 8. M. Kavun, 7. V. Fedorova, and M. N. Malev, Runner Cina. TecuwoL. 46, 575 (1973), *D. P. Graves, RunpeR CHEm. TecHNoL. 66, 61 (1993) 40M. L. Studebaker, RuaBeR Cnem. TECHNOL. 30, 1400 (1957), J.B Donnet and A. Voet, "Carbon Black. Physics, Chemistry and Elastomer Reinforcement,” M. Dekker. New York, 1976. "A, Schallamach, Russen CveM. TecunoL. 91, 892 (1958). "RJ. Cremlyn, J. Chem. Soc., 1132 (1965). “J, de Benito, L. Ibarra, and L, Gonzalez, Kausch. Gummi Kunstst. 43, 146, 697 (1990). * L, Gonaflez, A. Rodriguez, and J. L. de Benito, RunBER CHEM, TECHNOL 65, 869 (1992), "J. A. Ayala, W. M. Hess, A. O. Dotson, and G. A. Joyce, Rusnen Cie. TecMNot. 63, 747 (1190) 1 Y. Saito, Kautsch. Gummi Kunstst 39, 30 (1986). % J. Fujimaki, M. Ogawa, S. Yamaguchi, 8, Tomita, and M. Okuyama, Proc. Int, Rubber Conf., Tokyo, 1985, p. 184 * L. Gonailez, A. Rodriguez, J. L. de Benito, and A. Marcos, patent in preparation, [Received Nov. 9, 1995; revised Jan. 2, 1996)