The Effective Parameters in the Synthesis of N-(1, 3-Dimethylbutyl)-N'-Phenyl-p-Phenylenediamine as Antiozonant and Antioxidant for Natural and Synthetic Elastomers

Document Type : Research Article


Chemistry & Petrochemical Division, Research Institute of Petroleum Industry (RIPI), Teheran, I.R. IRAN


N-(1, 3-Dimethylbutyl)-N'-phenyl-1, 4-phenylenediamine (Santoflex 6PPD) functions as a powerful antioxidant and antiozonant for natural and synthetic elastomeric compounds and as synthetic polymer stabilizer. Santoflex 6PPD provides protection against different forms of aging and fatigue degradation of flexible rubber components in both static and dynamic operation conditions at high temperature during storage and service operation is essential. In this research synthesis of this compound from 4-AminoDiPhenylAmine (4-ADPA) and Methyl IsoButyl Ketone (MIBK) in the presence of 5%Pt/C as catalyst with thermodynamic variables (temperature, pressure) and kinetic parameters (stirring speed, reaction time, and molar ratio) were examined with an oxidizer. At first, (4-nitrodiphenyl amine and 4-nitrosodiphenyl amine) were prepared by direct  coupling of  aniline and nitrobenzene under optimized molar  ratio of hydrogen peroxide to moles nitrobenzene in the presence of a strong base. Then 4-ADPA was synthesized under hydrogen pressure about 200-220 psig at 80 °C in the presence of 5%Pt/C as catalyst with efficiency increase about 10% and by product reduce compared to conventional methods. In the second step, 4-ADPA was reacted with Methyl IsoButyl Ketone (MIBK) under hydrogen pressure of about 800 psig and temperature of 170-175 °C in the presence of 5% Pt/C catalyst Santo flex 6PPD was synthesized in 99% purity and the yield of reaction was 95% with efficiency increase about 3% in comparison with conventional methods. All of the synthesized compounds were ‍characterized by FT-IR, 1HNMR, C.H .N. and G.C. analysis.


Main Subjects

[1] Datta R.N., Talma A.G., Bathmen, Rubber Vulcanizates Having Improved Ageing Properties, USP 2001/0031836A1(2002).
[2] Keller R.W., Degradation of Ethylene-Propylene Elastomers in the Presence ofOzone, Rubber Chem. Technol., 58, p. 637(1985).
[3] Zhao J., Ghebremeskel G.N., A Review of Some of the Factors Affecting Fracture and Fatigue in SBR and BR Vulcanizates, Rubber Chem. Technol., 74, p. 409(2001).
[4] Erhardt D., Enviromental Resistance, Int. Polym. Sci. Technol., 25, p. 11(1998).
[5] Rakovski S.K., Cherneva D. R., Durability of Rubber Products, Int. J. Polym. Mater., 14, p. 21(1990).
[6] Scott G.,Initiation Processes in Polymer Degradation, Rubber Chem. Technol., 58, p. 269(1985).
[7] Bolland J.L., Quart. Rev.,Photo Chemistry of Man-Made Polymers, Chem. Soc., 3, p. 1(1949).
[8] Shelton J.R., Vincent D.N., Kinetic of Radical Polymerization, J. Am. Chem. Soc., 85, p. 2433(1963).
[9] Bateman L., Cain M., Colclough T., Cunneen J.I., Oxidation of Organic Solphides, Part XIII, The Anioxidant Action of Sulphoxides and Thisulphinates in Autooxidang Squalene, J. Chem., Soc., p. 3570(1962).
[10] Ambelang J.C., Kline R.H., Lorenz O.M., Parks C.R., Wadelin C., Antioxidants and Antiozonants for General Purpose Elastomers, Rubber Chem. Technol., 36, p. 1497(1963).
[11] Saito Y., Ozonalysis of Model Olefins -Efficiency of Anti-Ozonants, Int. Polym. Sci. Technol., 22, p. 47(1995).
[12] Bruck D., Konigshofen H., Ruetz L., The Action of Antiozonants in Rubber, Rubber Chem. Technol., 58, p. 728 (1985).
[13] Bailey P.S., "Ozonation in Organic Chemistry", Academic Press, New York, 39.1(1978).
[14] Ho K.W., Ozonation of Hydrocarbon Diene Elastomers: a Mechanistic Study, Journal of Polymer Science Part A: Polymer Chemist, 24(10), p. 2467(1986).
[15] Hong S.W., Greene P.K., Lin C.Y., Durability of Rubber Products, Paper 65, ACS Rubber Division 155th Conference, Chicago, IL(1999).
[16] Latimer R.P., Hooser E.R., Layer R.W., Rhee C.K., Mechanisms of Ozonation of N,N′-di- (1-Methylheptyl)- p-Phenylenediamine, Rubber Chem. Technol., 53, p. 1170(1980).
[17] Latimer R.P., Hooser E.R., Layer R.W., Rhee C. K., Amines, Aromatic, Phenylenediamines, Rubber Chem. Technol., 56, p. 431(1983).
[18] Stren M.K., Bashkin, J.K., (to Monsanto), Method of Preparing 4-Aminodiphenylamine, USP 5117063(1992).
[19] Stern M.K., Bashkin J.K., (to Monsanto), Method of Preparing 4-Aminodiphenylamine,USP 5453541(1996).
[20] Stern M.K., Bashkin J.K., (to Monsanto), Process for Preparing N-Aliphatic Substituted P-Phenylenediamine, USP 5252737(1993).
[21] Stern M.K., Bashkin J.K., (to Monsanto), Process for Preparing p-Nitro Aromatic Aamide and Products Thereof, USP 5331099(1994).
[22] Stern M.K., Chang K.M., (to Monsanto), Process for Preparing Substituted Aromatic Azo Compounds, USP 5552531(1996).
[23] Stern M.K., Chang K.M., (to Monsanto), Process for Preparing Substituted Aromatic Amines, USP 5633407(1997).
[24] Solodar (to Monsanto), Preparation of Substituted Aromatic Amines, USP 4760186(1988).
[25] Stren M K., Chang K.M., (to Monsanto), Process for Preparing Substituted Aromatic Amines, USP5382691(1995).
[26] Stren M.K., Chang K.M., (to Monsanto), Process for Preparing Substituted Aromatic Amines, USP5618979(1997).
[27] Eok Kim J., Park J.C., Sun Lee K., Method for Preparing 4 Aminodiphenyl Amine, USP0258887A1(2006).
[28] Triplett II R.D., Rains R.G., Process for Preparing 4 Amino Diphenyl Amine Intermediate,USP 0191641 A1(2007).
[29] Fongy W.S., N-(1,3-Dimethyl Butyl)-N'-Phenyl-P-Pheylenediumine via a Novel 4-Nitrodiphenylamine and 4-Nitro Diphenylamine, Process Economics Progres (PEP), PEP 92-2-3, SRI International(1993).
[30] Stren M.K., Hileman F.D., Bashkin J.K, Direct Coupling of Aniline and Nitrobenzene: A New Example of Nucleophilic Aromatic Substitution for Hydrogen, J. Am. Chem. Soc., 114, p. 9237(1992).
[31] Triplett II R.D., Rains R.K., Process for Preparing 4-Aamino Diphenyl Amine Intermediate, US P0110986(2004).
[32] Triplett II R.D., Rains R.K., Process for Preparing 4-Amino Diphenyl Amine Intermediate, USP6395933B1(2002).
[33] Reinartz K., Brill A., Schuhmacher F., Process for the Preparation of Optionally Substituted 4 Aminodiphenylamine, USP 5739403(1998).
[34] Feng X., Wang N., Mao X., Yu R., Chen Q., Process for the Preparation 4-Amino Diphenylamine, USP 0048465A1(2009).
[35] “Ulmans Encyklopd”, Die Der Technischen Chemie, 4th Edition, Vol. 13, p.141(1985).
[36] Chen B., Arunajatesan V., Morrow J.L., Catalytic Reductive Alkylation of Aromatic and Alkyl Amines and Diamines over Sulfided and Unsulfided Platinum Group Metals, in: Michael Pronier (Ed.), "Catalysis of Organic Reaction", CRC Press (Michael Pronier (EDS.)), p.159(2008).