Ind. Eng. zyxwvutsrqpo Chem. Prod. Res. Dev. zyxwvu 1985, zyxwvu 24, 171-175 171 . . 6'= zyxwvutsrqponmlkjih Dl/Do zyxwvutsr v = molar volume, cm3/mol vf = free volume, cm3/mol vo = occupied volume, cm3/mol Superscripts 0 = global, observable m = ultimate, asymptotic Subscripts E = epoxide zyxwvutsrq A = amine 0 = initial (except for zyxwvutsrq yo, see above) Do = constant in Doolittle equation, cmz/s f = fractional free volume, zyxwvutsrq vf/v fg = fractional free volume at Tg zyxwvut kI = impurity-catalyzed rate constant, s-l kp = autocatalytic rate constant, s-l R = equivalents ratio, CAO/CEO T, = cure temperature, K Tg = glass-transition temperature, K Greek Letters CY = fractional conversion of epoxide rings, 1 - CE/C~O CY^ = thermal expansion coefficient of free volume, K-' iu, = da,/dt = reduced rate (da/dt)/(l - a)(R - CY) Carberry, J. J. "Chemical and Catalytic Reaction Englneering;" McGraw-Hill: Chung, H. S. J. Chem. Phys. 1966. 44(4), 1365. Cohen, M. H.; Turnbull, D. J. Chem. Phys. 1959, 37(5), 1164. Dannenberg, H. SOC.P/ast. Eng. Trans. 1963, 3(1), 78. De Gennes, P. G. J. Chem. Phys. 1971, 55(2), 572. De Gennes, P. G. J. Chem. Phys. 1982a, 76(6), 3316. De Gennes, P. G. J. Chem. Phys. 1982b, 76(6), 3322. Doolittie, A. K. J. Appl. Phys. 1951, a2(12), 1471. Doolittle, A. K. J. Appl. Phys. 1952, 23(2), 236. Doollttle, A. K. J. Appl. Phys. 1857, 28(8), 901. Dusek, K.; Bieha, M. J. Polym. Sci.. Polym. Ed. 1077, 75(1), 2393. Dusek, K.; Ilavsky, M.; Lunak, S. J. Polym. Sci., Symposium 1975, 53, 29. Fava, R. A. Polymer (London) 1968, 9(3), 137. Harrcd, J. F. J. Appl. Polym. Sci. 1962, 6(24), 563. Horle. K.; Hiura, M.; Sawada, M.; Mita, I.; Kambe, H. J. Polym. Sci., Part New York, 1976. A-7 1970. 8. 1357. Horle, K.; M&, I.; Kambe, H. J. Polym. Sci., Part A-7 W68, 6, 2663. Huguenin, G. A. E. MChE Thesis, University of Delaware, 1984. Isaacs, N. S.; Parker, R. E. J. Chem. SOC. 1960, 82, 3497. Kakurai, T.; Noguchi, T. Kogyo Kagaku Zasshi 1960, 63, 294. Kakurai, T.; Noguchi, T. Kogyo Kagaku Zasshi 1961. 64, 398. Kwei, T. K. J. Polym. Scl., Part A-2 1966, 4, 943. Kwei. T. K. J. Polvm. Sci., Part A 1983. 7, 2985. Lipatov, Y. Adv. Polym. Scl. 1977, 26, 63. Macedo, P. B.; Litovitz, T. A. J. Chem. Phys. 1985, 42(1), 245. Murayama, T.; Bell, J. P. J. Polym. Sci., Part A -2 1970, 8, 437. North, A. M.; Reed, G. A. J. Polym. Sci., Part A-2 1963, 7, 1311. O'Neii, L. A.; Cole, C. P. J. Appl. Chem. 1956, 6, 356. Prime, R. B.; Sacher, E. Polymer 1972, 73, 1972. Rabinowitch, E. Trans. Faracky SOC. 1937, 33, 1225. Shechter, L.; Wynstra. J.; Kurkjy, R. P. Ind. Eng. Chem. 1956, 48(1), 94. Smith, I. T. Polymer 1961, 2, 95. Sourour, S.; Kamal, M. R. Thermochim. Acta 1976, 74, 41. Tuiiig, T. J.; Tirrel, M. McromoLscules 1981, 14, 1501. Vrentas, J. S.; Duda, J. L. AIChE J. 1979, 25(1), 1. Williams, M. L.; Landel, R. F.; Ferry, J. D. J. Am. Chem. Soc. 1955, 77, Registry No. (Bisphenol A).(epichlorohydrin)(copolymer), 25068-38-6; 4,4'-diaminodiphenylmethane, 101-77-9. 3701. Literature Cited Acitelli, A.; Prime, M. A.; Sacher, E. Polymer 1971. 72, 335. Bell, J. P. J. Polym. Sci., Part A-2 1970. 6. 417. Bravenec, L. D. PhD. Thesis, University of Delaware, 1983. Bueche, F. J. Chem. Phys. 1962, 36(11), 2940. Received for review July 5, 1984 Accepted November 8, 1984 Evaluation of Aromatic Extracts as Antioxidants for Mineral Oils Dhoalb A. AI-Sammerral' and Mahmood M. Barbootl Petroleum Research Centre, Jadiriyah, Baghdad, Iraq Two aromatic extracts separated from light (grade 40) and heavy (grade 60) oil distillates by a selective solvent (furfural) were evaluated as oxidation inhibitors for sulfur-free and sulfur-containing refined mineral oils. The effectiveness of various concentrations of these extracts in preventing oxldation of the oil samples under oxidizing conditions was studied statically by differential scanning calorimetery (DSC) and dynamically by a catalytic oxidation test procedure. The results obtained from these two methods of evaluation correlated well. The grade 40 and 60 extracts Imparted good antioxidant protection to the sulfurcontaining mineral oil. The grade 60 extract exhibited a similar behavior In the sulfur-free oil, while the grade 40 extract could not be regarded as an efficient antioxidant for the same oil. Wh the aid of aromatic extracts it is possible to improve substantially lubricants of various types, particularly with regard to their resistance to oxidative attacks. Introduction The quality of lubricating oil distillates is improved by solvent extraction processes, which remove the poly- aromatic fractions and those more polar species that im- part instability. The distillate is usually contacted with a selective solvent such as furfural or phenol to provide a higher viscosity index raffinate and an aromatic extract from both of which the solvent is recovered (Berridge, 1975). The aromatic extracts are dark oils containing asphaltic residues. The composition of the extract is dependent on the extractive power of the solvent, operating parameters, and the type of distillate being extracted, but in normal refinery operation the extract would be expected to contain a196-4321/85/1224-0171801.5afa about 70 wt 90 and upward of aromatic compounds (Biske, 1975). Sulfur, nitrogen, and oxygen compounds concen- trated in the extract are mainly in heterocyclic ring structures. Owing to their high aromatic character, the extracts have a useful solvent power (Nejak, 1968). This led to their utilization as extenders in rubber and plastic compositions and as a partial replacement for linseed oil in paints and varnishes. A variety of organic chemical compounds have been used as oxidation inhibitors in lubricating oils (Molyneux, 1967). These include sulfur compounds, amines, and phenolic derivatives. Polyaromatic fractions separated chromato- graphically from refined mineral oils (AI-Sammerrai et al., 0 1985 American Chemical Society