Zinc Surfactant Effects on Nr/Tespd/Silica and SBR/Tespd/Silica Compounds

  • Published : 2004.12.31


The effects of zinc surfactant (ZB) on the bis(triethoxysilylpropyl)disulfide (TESPD)-silica mixture in natural rubber (NR) and solution butadiene-co-styrene rubber(S-SBR) were compared with respect to their rheological property, processability, physical properties, and silica dispersion. In the NR compound, addition of the ZB increased the reversion resistance time (T-2), the tensile modulus, and the BO time; however, lowered the viscosity, the HBU, and tans values. In the S-SBR copound, addition of the ZB increased the $tan{\delta}$ values while lowered the T-2, the tensile modulus the BO time, the viscosity, and the HBU of the compound. In the NR compounds, addition of the ZB significantly increased the processability and mechanical property. However, in the S-SBR compounds, it improved the processability the mechanical property was not improved.


  1. F. Thurn and S. Wolff, 'Neue Organosilane fur die Reifenindustrie', Kautsch. Gummi Kunstst., 28, 733 (1975)
  2. S. Wolff, 'A New Development for Reversible Sulfur-Cured NR Compounds', Kautsch. Gummi Kunstst., 32, 760 (1979)
  3. A. Hunsche, U. Gorl, A. Muller, M. Knaack, Th. Gobel, and Hurth, 'Investigatins Concerning the Reaction Silica/Organosilane and Organosilane/Polymer', Kautsch. Gummi Kunstst., 50, 881 (1997)
  4. R. Rauline (Michelin), Europe Patent EP0501 227, (1991)
  5. R. Rauline (Michelin), U.S. Patent (filed Feb. 20,1992) 5,227,425 (1993)
  6. Anonymous, 'Rubber Industry Manual', Bayer A. G., 1993
  7. J. H. Bachmann, J. W. Sellers, and M. P. Wagner, 'Fine Particle Reinforcing Silicas and Silicates in Elastomers', Rubber Chem. Technol., 32, 1286 (1959)
  8. E. M. Dannenberg, 'The Effects of Surface Chemical Interactions on the Properties of Filler-Reinforced Rubbers', Rubber Chem. Technol., 48, 410 (1975); 'Reinforcement of Silicone Rubber by Particulate Silica', Rubber Chem. Technol., 48, 558 (1975)
  9. M. P. Wagner, 'Reinforcing Silicas and Silicates', Rubber Chem. Technol., 49, 703 (1976)
  10. P. Vondracek, M. Hradec, V. Chvalovsky, and H.D. Khanh,' The Effect of the Structure of Sulfur Containing Silane Coupling Agents on Their Activity in Silica-Filled SBR', Rubber Chem. Technol., 57, 675 (1984)
  11. A. Krysztafkiewicz, 'Modified Silica Precipitated in the Medium of Organic Solvents-an Active Rubber Filler', Colloid Polym. Sci., 267, 399 (1989) https://doi.org/10.1007/BF01410184
  12. S. Kohjiya and Y. Ikeda, 'Reinforcement of General-Purpose Grade Rubbers by Silica Generated In Situ', Rubber Chem. Technol., 73, 534 (2000)
  13. K. J. Kim and J. L. White, 'TESPT and Different Aliphatic Silane Treated Silica Compounds Effects on Silica Agglomerate Dispersion and on Processability During Mixing in EPDM', J. Ind Eng. Chem., 7, 50 (2001)
  14. J. A. Hockley, and B. A. Pethica, 'Surface Hydration of Silicas', Faraday Soc. Trans., 57, 2247 (1961) https://doi.org/10.1039/tf9615702247
  15. D. R. Bassett, E. A. Boucher, and A. C. Zettlemoyer, 'Adsorption on Hydrated and Dehydrated Silicas', J. Colloid Interface Sci., 27, 649 (1968) https://doi.org/10.1016/0021-9797(68)90097-0
  16. K. J. Kim, and J. L. White, 'Silica Agglomerate Breakdown in Three-Stage Mix Including A Continuous Ultrasonic Extruder', J. Ind Eng. Chem., 6(4), 262 (2000)
  17. K. J. Kim, and J. VanderKooi, 'TESPT and TESPD Treated Silica Compounds on Rheological Property and Silica Break Down in Natural Rubber', Kautsch. Gummi Kunstst., 55(10), 518 (2002)
  18. K. J. Kim and J. VanderKooi, 'Rheological Effects of Zinc Surfactant on the TESPT-Silica Mixture in NR and S-SBR Compounds', Int. Polym. Process., 17, 192 (2002)
  19. K. J. Kim and J. VanderKooi, 'Effects of Zinc Ion Containing Surfactant on Bifunctional Silane Treated Silica Compounds in Natural Rubber', J. Ind Eng. Chem., 8(4), 334 (2002) https://doi.org/10.1021/i500004a015
  20. A. D. Roberts Ed., 'Natural Rubber Science and Technology', Oxford Science Publications, New York, 1988
  21. S. Montes, J. L. White, and N. Nakajima, 'Rheological Behavior of Rubber Carbon Black Compounds in Various Shear Flow Histories', J.Non-Newtonian Fluid Mech., 28, 183 (1988) https://doi.org/10.1016/0377-0257(88)85039-0
  22. J. L. White, 'Rubber Processing: Technology, Materials, and Principles', Hanser Publishers, Cincinnati, 1995
  23. A. N. Gent, 'Engineering with Rubber: How to Design Rubber Components', Hanser Publishers, New York, 1992
  24. R. W. Allen (Firestone Tire & Rubber Co.), U.S. Patent (filed June 9, 1931) 02,048,314 (1936)
  25. E. P. Plueddemann, 'Silane Coupling Agents', Plenum Press, New York, 1982
  26. S. Wolff, 'Vernetzung von 1,5-Dien-Kautschuken mittels Bis-(3-triathoxysilylpropyl)-tetrasulfid', Kautsch. Gummi Kunstst., 30, 516 (1977)
  27. S. Wolff, 'Fullstoffentwicklung Heute und Morgen', Kautsch. Gummi Kunstst., 32, 312 (1979)
  28. S. Wolff, 'Reinforcing and Vulcanization Effects of Silane Si69 in Silica-Filled Compounds', Kautsch. Gummi Kunstst., 34, 280 (1981)
  29. S. Wolff, 'Optimization of Silane-Silica OTR Compounds. Part 1: Variations of Mixing Temperature and Time During The Modification of Silica with Bis-(3-triethoxisilylpropyl)-tetrasulfide', Rubber Chem. Technol., 55, 967 (1982)
  30. C. Lin, W. L. Hergenrother, and A. S. Hilton, 'Mooney Viscosity Stability and Polymer Filler Interactions in Silica Filled Rubbers', Rubber Chem. Tecnol., 75, 215 (2002) https://doi.org/10.5254/1.3544974
  31. E. H. Tan, S. Wolff, M. Haddernan, H. P.Grewatta, and M. J. Wang, 'Filler-Elastomer Interactions. Part 1X. Performance of Silicas in Polar Elastomers', Rubber Chem. Technol., 66,594 (1993)
  32. E. Sheng and I. Sutherland, 'A Quantitative XPS Study of Spherically Shaped Powders Coated with an Overlayer', Surface Sci., 314, 325 (1994) https://doi.org/10.1016/0039-6028(94)90234-8
  33. B. Haworth, C. L. Raymond, and I. Sutherland, 'Polyethylene Compounds Containing Mineral Fillers Modified by Acid Coatings. 1: Characterization and Processing', Polym. Eng. Sci., 40, 1953 (2000) https://doi.org/10.1002/pen.11327
  34. K. J. Kim and J. L. White, 'Silica Surface Modification Using Different Aliphatic Chain Length Silane Coupling Agents and Their Effects on Silica Agglomerate Size and Processability'', Composite Interfaces, 9(6), 541 (2002) https://doi.org/10.1163/15685540260494119
  35. U. Goerl, A. Hunsche, A. Mueller, and H. G. Koban, 'Investigations into the Silica/Silane Reaction System', Rubber Chem. Technol., 70, 608 (1997). https://doi.org/10.5254/1.3538447
  36. K. J. Kim and J. VanderKooi, 'Improved Polymer Processing for Critical Extrusions', ITEC 2002 Akron OH (No. 7A)
  37. C. W. Bunn, 'Molecular Structure and Rubber-Like Elasticity: I. The Crystal Structure of B Gutta-Percha, Rubber and Polychloroprene', Proc. Roy. Soc. A, 180, 40 (1942) https://doi.org/10.1098/rspa.1942.0024
  38. B. Wunderlich, 'Macromolecular Physics, Vol 2', Academic Press, New York, (1978)
  39. M. Avrami, 'Kinetics of Phase Change. I', J.Chem. Phys., 7, 1103 (1939) https://doi.org/10.1063/1.1750380
  40. M. Avrami, 'Kinetics of Phase Change. II Transformation-Time Relaxation for Random Distribution of Nuclei', J. Chem. Phys., 8, 212 (1940) https://doi.org/10.1063/1.1750631
  41. M. Avrami, 'Kinetics of Phase Change. III Granulation, Phase Change, and Microstructure', J.Chem. Phys., 9, 177 (1941) https://doi.org/10.1063/1.1750872
  42. A. N. Gent, 'Crystallization and the Relaxation of Stress in Stretched Natural Rubber Vulcanizates', Faraday Soc. Trans., 50, 521 (1954) https://doi.org/10.1039/tf9545000521
  43. A. N. Gent, 'Crystallization in Natural Rubber. IV. Temperature Dependence', J. Polym. Sci., 18, 321 (1955) https://doi.org/10.1002/pol.1955.120188901
  44. P. J. Flory, 'Thermodynamics of Crystallization in High Polymers: I. Crystallization Induced by Stretching', J. Chem. Phys., 15, 397 (1947) https://doi.org/10.1063/1.1746537
  45. E. H. Andrews, 'Crystalline Morphology in Thin Films of Natural Rubber: II. Crystallization Under Strain', Proc. Roy. Soc. A, 277, 562 (1964) https://doi.org/10.1098/rspa.1964.0040
  46. E. H. Andrews, 'Spherulite Morphology in Thin Films of Natural Rubber', Proc. Roy. Soc. A, 270, 232 (1962) https://doi.org/10.1098/rspa.1962.0214
  47. A. Keller, and M. J. Machin, 'Oriented Crystallization in Polymers', J. Macromol. Sci., Bl,41 (1967)
  48. J. D. Hoffmann, J. I. Lauritzen, E. Passaglia, G.S. Ross, L. J. Frolen, and J. J. Weeks, 'Kinetics of Polymer Crystallization from Solution and the Melt', Koll. Z. Polym., 231, 564 (1969) https://doi.org/10.1007/BF01500015
  49. P. D. Calvert, and D. R. Uhlmann, 'Theory of Polymer Crystallization Chain Folding', J. Appl. Phys., 43, 944 (1972) https://doi.org/10.1063/1.1661311
  50. K. J. Smith, 'Crystallization of Networks under Stress', Polym. Eng. Sci., 16, 168 (1976) https://doi.org/10.1002/pen.760160309
  51. N. Bekkedahl, and L. A. Wood, 'Crystallization of Vulcanized Rubber', lnd. Eng. Chem., 33, 381 (1941) https://doi.org/10.1021/ie50375a023
  52. K. J. Kim and J. VanderKooi, 'Zinc Soap Effects on TESPT and TESPD Treated Silica Compounds on Processing and Silica Dispersion During Mixing in Natural Rubber', Paper presented at ACS: Rubber Division, Oct. 2001, Cleveland, OH(Paper No.79)