Rudnick L. Lubricant Additives: Chemistry and Applications (Присадки, добавки к смазкам)
Подождите немного. Документ загружается.
44 Lubricant Additives: Chemistry and Applications
69. Kelso, C.D. Phosphorus sulphide-hydrocarbon reaction product. U.S. Patent 2,315,529 (April 6, 1943,
Standard Oil Company).
70. Loane, C.M. and J.W. Gaynor. Lubricant. U.S. Patent 2,316,078 (April 6, 1943, Standard Oil
Company).
71. White, C.N. Lubricant. U.S. Patent 2,316,091 (April 6, 1943, Standard Oil Company).
72. May, R.L. Reaction products of aliphatic alcohols and terepene-phosphorus sulphide. U.S. Patent
2,356,073 (August 15, 1944, Sinclair Re ning Company).
73. May, R.L. Zinc salt of the reaction products of aliphatic alcohols and terepene-phosphorus sulphide.
U.S. Patent 2,356,074 (August 15, 1944, Sinclair Re ning Company).
74. Musselman, J.M. and H.P. Lankelma. Preparation of compounds for lubricants, etc. U.S. Patent 2,357,346
(September 5, 1944, The Standard Oil Company).
75. Berger, H.G., T.T. Noland, and E.W. Fuller. Mineral oil composition. U.S. Patent 2,373,094 (April 10,
1945, Socony-Vacuum Oil Company).
76. Mixon, L.W. Interface modi er. U.S. Patent 2,375,315 (May 8, 1945, Standard Oil Company).
77. Mixon, L.W. and C.M. Loane. Lubricant. U.S. Patent 2,377,955 (June 12, 1945, Standard Oil
Company).
78. May, R.L. Reaction products of alkylated phenols and terepene-phosphorus sulphide. U.S. Patent
2,379,312 (June 26, 1945, Sinclair Re ning Company).
79. Noland, T.T. Mineral oil composition. U.S. Patent 2,379,453 (July 3, 1945, Socony-Vacuum Oil
Company).
80. Hughes, E.C. and W.E. Scovill. Mineral oil bene ciation. U.S. Patent 2,381,907 (August 14, 1945, The
Standard Oil Company).
81. May, R.L. Lubricant. U.S. Patent 2,392,252 (January 1, 1946, Sinclair Re ning Company).
82. May, R.L. Lubricant. U.S. Patent 2,392,253 (January 1, 1946, Sinclair Re ning Company).
83. Musselman, J.M. and H.P. Lankelma. Lubricants. U.S. Patent 2,396,719 (March 19, 1946, The Standard
Oil Company).
84. Bartleson, J.D. Additives for lubricants. U.S. Patent 2,403,894 (July 9, 1946, The Standard Oil
Company).
85. May, R.L. Lubricating oil. U.S. Patent 2,409,877 (October 22, 1946, Sinclair Re ning Company).
86. Lincoln, B.H. and G.D. Byrkit. Lubricating oil. U.S. Patent 2,415,296 (February 4, 1947).
87. Berger, H.G. and E.W. Fuller. Mineral oil composition. U.S. Patent 2,416,281 (February 25, 1947,
Socony-Vacuum Oil Company).
88. Rogers, T.H., R.W. Watson, and J.W. Starrett. Lubricant. U.S. Patent 2,422,585 (June 17, 1947, Standard
Oil Company).
89. Fuller, E.W. and H.S. Angel. Mineral oil composition. U.S. Patent 2,455,668 (December 7, 1948, Socony-
Vacuum Oil Company).
90. Clason, D.L. and C.W. Schroeck. Phosphite treatment of phosphorus acid salts and compositions pro-
duced thereby. U.S. Patent 4,263,150 (April 21, 1981, The Lubrizol Corporation).
91. Rivier, G. Novel metallic dithiophosphates and their use as additives for lubricating oils. U.S. Patent
4,288,335 (September 8, 1981, Orogil).
92. Schroeck, C.W. Metal salts of lower dialkylphosphorodithioic acids. U.S. Patent 4,466,895 (August 21,
1984, The Lubrizol Corporation).
93. Clason, D.L. and C.W. Schroeck. Mixed metal salts and lubricants and functional uids containing
them. U.S. Patent 4,308,154 (December 29, 1981, The Lubrizol Corporation).
94. Sarin, R., D.K. Tuli, A.V. Sureshbabu, A.K. Misra, M.M. Rai, and A.K. Bhatnagar. Molybdenum dialky
lphosphorodithioates: synthesis and performance evaluation as multifunctional additives for lubricants.
Tribology International, 27(6), 379–86, 1994.
95. Lubricant additives. Technical Bulletin 506. (R.T. Vanderbilt Company Inc.).
96. Levine, S.A., R.C. Schlicht, H. Chafetz, and J.R. Whiteman. Molybdenum derivatives and lubricants
containing same. U.S. Patent 4,428,848 (January 31, 1984, Texaco Inc.).
97. Nalesnik, T.E. and C.A. Migdal. Oil-soluble molybdenum multifunctional friction modi er additives
for lubricant compositions. U.S. Patent 6,103,674 (August 15, 2000, Uniroyal Chemical Company Inc.).
98. Sarin, R., D.K. Tuli, V. Martin, M.M. Rai, and A.K. Bhatnagar. Development of N, P and S-containing
multifunctional additives for lubricants. Lubrication Engineering, 53(5), 21–27, 1997.
99. Ripple, D.E. Zinc-free farm tractor uid. PCT 2007005423 A2 (January 11, 2007, The Lubrizol
Corporation).
CRC_59645_Ch001.indd 44CRC_59645_Ch001.indd 44 12/4/2008 3:33:25 PM12/4/2008 3:33:25 PM
Antioxidants 45
100. Schadenberg, H. Dithiophosphate ester derivatives and their use for stabilizing organic material. British
Patent 1,506,917 (September 30, 1975), Shell International Research.
101. Davis, R.H., A. Okorodudu, and M. Sedlak. Lubricant compositions containing a dithiophosphoric
acid ester-aldehyde reaction product. European Patent Appl. 00090506 A2 (March 3, 1983, Mobil Oil
Corporation).
102. Braid, M. Lubricating oils or fuels containing adducts of phosphorodithioate esters. U.S. Patent
3,644,206 (February 22, 1972, Mobil Oil Corporation).
103. Rogers, T.H. Re ned viscous hydrocarbon oil. U.S. Patent 1,774,845 (September 2, 1930, Standard Oil
Company).
104. Rogers, T.H. Re ned viscous hydrocarbon oil. U.S. Patent 1,793,134 (February 17, 1931, Standard Oil
Company).
105. Roberts, E.N. Lubricant. U.S. Patent 2,409,799 (October 22, 1946, Standard Oil Company).
106. Jenkins, V.N. Diesel engine lubricating oil. U.S. Patent 2,366,191 (January 2, 1945, Union Oil Company
of California).
107. Dubois, L.O. and R.N. Gartside. Continuous manufacture of nitrobenzene. U.S. Patent 2,773,911
(December 11, 1956, E.I. du Pont de Nemours and Company).
108. Karkalits, O.C., Jr., C.M. Vanderwaart, and F.H. Megson. New catalyst for reducing nitrobenzene
and the process of reducing nitrobenzene thereover. U.S. Patent 2,891,094 (June 16, 1959, American
Cyanamid Co.).
109. Addis, G.I. Vapor phase process for the manufacture of diphenylamine. U.S. Patent 3,118,944 (January 21,
1964, American Cyanamid Co.).
110. Lai, J.T. and D.S. Filla. Process for production of liquid alkylated diphenylamine antioxidant. U.S.
Patent 5,750,787 (May 12, 1998, The B.F. Goodrich Company).
111. Popoff, I.C., P.G. Haines, and C.E. Inman. Alkylation of diphenylamine. U.S. Patent 2,943,112 (June
28, 1960, Pennsalt Chemicals Corporation)
112. Lai, J.T. Synthetic lubricant antioxidant from monosubstituted diphenylamines. U.S. Patent 5,489,711
(February 6, 1996, The B.F. Goodrich Company).
113. Lai, T.J. Lubricant composition. U.S. Patent 6,426,324 (July 30, 2002, Noveon IP Holdings Corp. and
BP Exploration & Oil Inc.).
114. Andress, H.J., Jr. and R.H. Davis. Arylamine-aldehyde lubricant antioxidants. European Patent Appl.
0083871 A2 (July 20, 1983, Mobil Oil Corporation).
115. Franklin, J. Liquid antioxidant produced by alkylating diphenylamine with a molar excess of diisobu-
tylene. U.S. Patent 4,824,601 (April 25, 1989, Ciba-Geigy Corporation).
116. Lai, J.T. Method of manufacturing alkylated diphenylamine compositions and products thereof.
U.S. Patent 6,204,412 (March 12, 2001, The B.F. Goodrich Company).
117. Lai, J.T. and D.S. Filla. Liquid alkylated diphenylamine antioxidant. U.S. Patent 5,672,752 (September 30,
1997, B.F. Goodrich Company).
118. Onopchenko, A. Alkylation of diphenylamine with polyisobutylene oligomers. U.S. Patent 6,355,839
(March 12, 2002, Chevron U.S.A. Inc.).
119. Braid, M. Lubricant compositions containing N-tertiary alkyl benzotriazoles. U.S. Patent 4,519,928
(May 28, 1985, Mobil Oil Corporation).
120. Shim, J. Lubricant compositions containing antioxidant mixtures comprising substituted thiazoles and
substituted thiadiazole compounds. U.S. Patent 4,260,501 (April 7, 1981, Mobil Oil Corporation).
121. Shim, J. Multifunctional additives. U.S. Patent 4,511,481 (April 16, 1985, Mobil Oil Corporation).
122. Shim, J. Triazole-dithiophosphate reaction product and lubricant compositions containing same.
U.S. Patent 4,456,539 (June 26, 1984, Mobil Oil Corporation).
123. Wright, W.E. Antioxidant diamine. U.S. Patent 4,456,541 (June 26, 1984, Ethyl Corporation).
124. Bandlish, B.K., F.C. Loveless, and W. Nudenberg. Amino compounds and use of amino compounds as
antioxidants in lubricating oils. European Patent 022281 B1 (September 14, 1983, Uniroyal Inc.).
125. Muller, R. and W. Hartmann. N,N′-Diphenyl-p-phenylenediamines, method for their production and
their use as stabilizers for organic materials. European Patent Appl. 072575 A1 (February 23, 1983,
Chemische Werke Lowi GmbH).
126. Colclough, T. Lubricating oil components and additives for use therein. U.S. Patent 5,232,614 (August 2,
1993, Exxon Chemical Patents Inc.).
127. Malherbe, R.F. 2,3-Dihydroperimidines as antioxidants for lubricants. U.S. Patent 4,389,321 (June 21,
1983, Ciba-Geigy Corporation).
CRC_59645_Ch001.indd 45CRC_59645_Ch001.indd 45 12/4/2008 3:33:25 PM12/4/2008 3:33:25 PM
46 Lubricant Additives: Chemistry and Applications
128. Roberts, J.T. N,N′-Disubstituted 2,4′-diaminodiphenyl ethers as antioxidants. U.S. Patent 4,309,294
(January 5, 1982, UOP Inc.).
129. Roberts, J.T. Imines of 2,4-diaminodiphenyl ethers as antioxidants for lubricating oils and greases.
U.S. Patent 4,378,298 (March 29, 1983, UOP Inc.).
130. Sung, R.L. and B.H. Zoleski. Diesel lubricant composition containing 5-amino-triazole-succinic
anhydride reaction product. U.S. Patent 4,256,595 (March 17, 1981, Texaco Inc.).
131. Braid, M. Phenolic antioxidants and lubricants containing same. U.S. Patent 4,551,259 (November 5,
1985, Mobil Oil Corporation).
132. McKinnie, B.G. and P.F. Ranken. (Hydrocarbylthio)phenols and their preparation. U.S. Patent 4,533,753
(August 6, 1985, Ethyl Corporation).
133. Gatto, V.J. and A. Kadkhodayan. Sulfurized phenolic antioxidant composition method of preparing same
and petroleum products containing same. U.S. Patent 6,001,786 (December 14, 1999, Ethyl Corporation).
134. Dong, J. and C.A. Migdal. Synergistic antioxidant systems for lubricants. 12th Asia Fuels and Lubes
Conference Proceedings. Hong Kong, 2006.
135. Braid, M. Phenolic antioxidants and lubricants containing the same. U.S. Patent 4,551,259 (November 5,
1985, Mobil Oil Co.).
136. Gatto, V.J. Hydroxyphenyl-substituted amine antioxidants. U.S. Patent 5,292,956 (March 8, 1994, Ethyl
Corporation).
137. Nelson, L.A. and L.R. Rudnick. Mannich type compounds as antioxidants. U.S. Patent 5,338,469
(August 16, 1994, Mobil Oil Corporation).
138. Oumar-Mahamat, H. and A.G. Horodysky. Phenolic imidazoline antioxidants. U.S. Patent 5,846,917
(December 8, 1998, Mobil Oil Corporation).
139. Camenzind, H., A. Dratva, and P. Hanggi. Ash-free and phosphorus-free antioxidants and antiwear
additives for lubricants. European Patent Appl. 894,793 (February 3, 1999, Ciba Specialty Chemicals
Holding Inc.).
140. Hsu, S.Y. and A.G. Horodysky. Sulfur-containing ester derivative of arylamines and hindered phenols
as multifunctional antiwear and antioxidant additives for lubricants. U.S. Patent 5,304,314 (April 19,
1994, Mobil Oil Corporation).
141. Andress, H.J. and H. Ashjian. Products of reaction involving alkenylsuccinic anhydrides with aminoal-
cohols and aromatic secondary amines and lubricants containing same. U.S. Patent 4,522,736 (June 11,
1985, Mobil Oil Corporation).
142. Nelson, K.D. and E.A. Chiverton. Fused aromatic amine based wear and oxidation inhibitors for
lubricants. U.S. Patent Application 2006/02237 A1 (October 5, 2006, Chevron Texaco Corporation).
143. Loper, J.T. Dispersant reaction product with antioxidant capability. U.S. Patent Appl. 2006/0128571
(June 15, 2006, Afton Corporation).
144. Migdal, C.A., T.E. Nalesnik, and C.S. Liu. Dispersant and antioxidant additive and lubricating oil
composition containing same. U.S. Patent 5,075,383 (December 24, 1991, Texaco Inc.).
145. Colclough, T. Lubricating oil oxidation and stabilization, in Atmospheric Oxidation and Antioxidants.
G. Scott ed., Elsevier Science Publishers B.V., Amsterdam, 1993.
146. Klaus, E.E., J.L. Duda, and J.C. Wang. Study of copper salts as high-temperature oxidation inhibitors.
Tribology Transactions, 35(2), 316–324, 1992.
147. Holt, D.G.L. Multiring aromatics for enhanced deposit control. European Patent Appl. 0709447 (May 1,
1996, Exxon Research and Engineering Company).
148. Colclough, T., F.A. Gibson, and J.F. Marsh. Lubricating oil compositions containing ashless disper-
sant, zinc dihydrocarbyldithiophosphate, metal detergent and a copper compound. U.S. Patent 4,867,890
(September 19, 1989).
149. Downing, F.B. and H.M. Fitch. Lubricant. U.S. Patent 2,343,756 (March 7, 1944, E.I. du Pont de Nemours &
Company).
150. Fox, A.L. Solution of Copper mercaptides from terpenes. U.S. Patent 2,349,820 (May 30, 1944, E.I. du
Pont de Nemours & Company).
151. Downing, F.B. and H.M. Fitch. Lubricating oil. U.S. Patent 2,356,661 (August 22, 1944, E.I. du Pont de
Nemours & Company).
152. Gurierrez, A., D.W. Brownawell, and S.J. Brois. Copper complexes of oxazolines and lactone oxazolines
as lubricating oil additives. U.S. Patent 4,486,326 (December 4, 1984, Exxon Research & Engineering
Co.).
153. Hopkins, T.R. Copper salts of succinic anhydride derivatives. U.S. Patent 4,552,677 (November 12,
1985, The Lubrizol Corporation).
CRC_59645_Ch001.indd 46CRC_59645_Ch001.indd 46 12/4/2008 3:33:25 PM12/4/2008 3:33:25 PM
Antioxidants 47
154. Farng, L.O. and A.G. Horodysky. Copper salts of hindered phenolic carboxylates and lubricants and fuel
containing same. U.S. Patent 4,828,733 (May 9, 1989, Mobil Oil Corporation).
155. Stanulov, K., H.N. Harbara, and G. Cholakov. Antioxidation properties of boron-containing lubricant
additives and their mixtures with Zn dialkyldithiophosphates. Oxidation Communications, 22(3),
374–386, 1999.
156. Yao, J.B. and J.X. Dong. Improvement of hydrolytic stability of borate esters used as lubricant additives.
Lubrication Engineering, 51(6), 475–479, 1995.
157. Horodysky, A.G. Borated epoxides and lubricants containing same. U.S. Patent 4,410,438 (October 18,
1983, Mobil Oil Corporation).
158. Horodysky, A.G. Borated hydroxyl-containing compositions and lubricants containing same. U.S. Patent
4,788,340 (November 29, 1998, Mobil Oil Corporation).
159. Farng, L.O. and A.G. Horodysky. Mixed hydroquinone-hydroxyester borates as antioxidants. U.S.Patent
4,828,740 (May 9, 1989, Mobil Oil Corporation).
160. Braid, M. Phenol-hindered phenol borates and lubricant compositions containing same. U.S. Patent
4,530,770 (July 23, 1985, Mobil Oil Corporation).
161. Koch, F.W. Boron-containing compositions and lubricants containing them. U.S. Patent 5,240,624
(August 31, 1993, The Lubrizol Corporation).
162. Yao, J.B., W.L. Wang, S.Q. Chen, J.Z. Sun, and J.X. Dong. Borate esters used as lubricant additives.
Lubrication Science, 14–4, 415–423, 2002.
163. Horodysky, A.G. Borated adducts of diamines and alkoxides, as multifunctional lubricant additives, and
compositions thereof. U.S. Patent 4,549,975 (October 29, 1985, Mobil Oil Corporation).
164. Horodysky, A.G. and J.M. Kaminski. Friction reducing additives and compositions thereof. U.S. Patent
4,298,486 (November 3, 1981, Mobil Oil Corporation).
165. Horodysky, A.G. and J.M. Kaminski. Friction reducing additives and compositions thereof. U.S. Patent
4,478,732 (October 23, 1984, Mobil Oil Corporation).
166. Horodsky, A.G. and R.S. Herd. Etherdiamine borates and lubricants containing same. U.S. Patent
4,537,692 (August 27, 1985, Mobil Oil Corporation).
167. Yao, J.B. and P. Ma. Interaction of organic borate ester containing nitrogen with other lubricant additives.
Lubricating Oil (Runhuayou), 21(2), 32–47, 2006.
168. Farng, L.O. and A.G. Horodysky. Lubricant composition containing phenolic/ phosphorodithioate borates
as multifunctional additives. U.S. Patent 4,956,105 (September 11, 1990, Mobil Oil Corporation).
169. Hinkamp, J.B., J.D. Bartleson, and G.E. Irish. Boron esters and process of preparing same. U.S. Patent
3,356,707 (December 5, 1967, Ethyl Corporation).
170. Braid, M. Borate esters and lubricant compositions containing such esters. U.S. Patent 4,547,302
(October 15, 1985, Mobil Oil Corporation).
171. Small, V.R., Jr., T.V. Liston, and A. Onopchenko. Diethylamine complexes of borated alkyl catechols and
lubricating oil compositions containing the same. U.S. Patent 4,975,211 (December 4, 1990, Chevron
Research Company).
172. Small, V.R., Jr., T.V. Liston, and A. Onopchenko. Diethylamine complexes of borated alkyl catechols
and lubricating oil compositions containing the same. U.S. Patent 5,061,390 (October 29, 1991, Chevron
Research Company).
173. Wright, W.E. and B.T. Davis. Haze-free boronated antioxidant. U.S. Patent 4,927,553 (May 22, 1990,
Ethyl Corporation).
174. Brown, J.R., P.E. Adams, V.A. Carrick, B.R. Dohner, W.D. Abraham, J.S. Vilardo, R.M. Lange, and P.E.
Mosier. Titanium compounds and complexes as additives in lubricants. U.S. Patent Appl. 2006/0217271
(September 28, 2006, The Lubrizol Corporation).
175. Esche, C.K., Jr. Additives and lubricant formulations for improved antioxidant properties. U.S. Patent
Appl. 2006/0205615 (September 14, 2006, New Market Services Corporation).
176. Ravichandran, R., F. Abi-Karam, A. Yermolenka, M. Hourani, and I. Roehrs. Amine tungstates and
lubricant compositions. WO 2007/009022 A2 (January 18, 2007, King Industries Inc.).
177. Gatto, V.J. and M.T. Devlin. Lubricant containing molybdenum compound and secondary diarylamine.
U.S. Patent 5,650,381 (July 22, 1997, Ethyl Corporation).
178. Gatto, V.J. and M.T. Devlin. Lubricating composition. Great Britain Patent Application 2,307,245
(May 21, 1997, Ethyl Corporation).
179. Rasberger, M. Oxidative degradation and stabilisation of mineral oil based lubricants, in Chemistry
and Technology of Lubricants. R.M. Motier and S.T. Orszulik, eds., Blackie Academic & Professional,
London, UK, 98–143, 1997.
CRC_59645_Ch001.indd 47CRC_59645_Ch001.indd 47 12/4/2008 3:33:25 PM12/4/2008 3:33:25 PM
48 Lubricant Additives: Chemistry and Applications
180. Paolino, P.R. Antioxidants, in Thermoplastic Polymer Additives. J.T. Lutz Jr., ed., Marcel Dekker, Inc.,
New York, 1–35, 1989.
181. Reyes-Gavilan, J.L. and P. Odorisio. NLGI Spokeman, 64(11), 22–33, 2001.
182. Pospisil, J. Aromatic and heterocyclic amines in polymer stabilization. Advances in Polymer Science,
124, 87–190, 1995.
183. Lowry, T.H. and K.S. Richardson. Mechanism and theory, in Organic chemistry. Harper and Row
Publishers, New York, 472, 1976.
184. Colclough, T. Role of additives and transition metals in lubricating oil oxidation. Industrial & Engineer-
ing Chemistry Research, 26, 1888–1895, 1987.
185. Maleville, X., D. Faure, A. Legros, and J.C. Hipeaux. Oxidation of mineral base oils of petroleum
origin: The relationship between chemical composition, thickening, and composition of degradation.
Lubrication Science, 9, 3–60, 1996.
186. Jensen, R.K., S. Korcek, L.R. Mahoney, and M. Zinbo. Liquid–phase autoxidation of organic com-
pounds at elevated temperatures. 1. The stirred ow reactor technique and analysis of primary prod-
ucts from n-hexadecane autoxidation at 120–180°C. Journal of the American Chemical Society, 101,
7574–7584, 1979.
187. March, J. The aldol condensation, in Advanced Organic Chemistry, 3rd edn., John Wiley & Sons, Inc.,
New York, pp. 829–834, 1985.
188. Hamblin, P.C. and P. Robrbach. Piston deposit control using metal-free additives. Lubrication Science,
14(1), 3–22, 2001.
189. Sequeira, A., Jr. Crude oils, base oils, and petroleum wax, in Lubricant Base Oil and Wax Processing.
Marcel Dekker, Inc., New York, 1994.
190. Demarco, N. Global supply: links and kinks. Lubes’N’Greases, April, 15–18, 2007.
191. Murray, D.W., C.T. Clarke, G.A. MacAlpine, and P.G. Wright. The effect of base stock composition on
lubricant performance, SAE Technical Paper 821236.
192. Cerny, J., M. Pospisil, and G. Sebor. Composition and oxidative stability of hydrocracked base oils and
comparison with a PAO. Journal of Synthetic Lubrication, 18(3), 199–213, 2001.
193. Kramer, D.C., J.N. Ziemer, M.T. Cheng, C.E. Fry, R.N. Reynolds, B.K. Lok, M.L. Sztenderowicz, and
R.R. Krug. In uence of group II & III base oil composition on V.I. and oxidative stability. Presented at
the 66th NLGI Annual Meeting, Tucson, AZ, October, 1999.
194. Igarashi, J., T. Yoshida, and H. Watanabe. Concept of optimal aromaticity in base oil oxidative stability
revisited. Symposium on Worldwide Perspectives on the Manufacture, Characterization and Application
of Lubricant Base Oils: 213th Annual Meeting Preprint, American Chemical Society, San Francisco,
CA, April 13–17, 1997.
195. Wang, H.D. and X.L. Hu. The study advance on effects of molecular structure of group II, III base oils
on the oxidation stability. Lubricating Oil, 20(2), 10–14, 2005.
196. Adhvaryu, A., S.Z. Erhan, and I.D. Singh. The effect of molecular composition on the oxidative behavior
of group I base oils in the presence of an antioxidant additive. Lubrication Science, 14(2), 119–129, 2002.
197. Yoshida, T., J. Igarashi, H. Watanabe, A.J. Stipanovic, C.Y. Thiel, and G.P. Firmstone. The impact
of basic nitrogen compounds on the oxidative and thermal stability of base oils in automotive and
industrial applications. SAE Paper 981405, 1998.
198. MacFaul, P.A., K.U. Ingold, and J. Lusztyk. Kinetic solvent effects on hydrogen atom abstraction
from phenol, aniline, and diphenylamine. The importance of hydrogen bonding on their radical- trapping
(antioxidant) activities. Journal of the Organic Chemistry, 61, 1316–1321, 1996.
199. Hamblin, P.C., D. Chasan, and U. Kristen. A review: ashless antioxidants, copper deactivators and
corrosion inhibitors. Their use in lubricating oils, in 5th International Colloquium on Additives for
Operational Fluids, J Bart zed., Technische Akademie Esslingen, 1986.
200. Boozer, C.E., G.S. Hammond, C.E. Hamilton and J.N. Sen. Air oxidation of hydrocarbons II. The
stoichiometry and fate of inhibitors in benezene and chlorobenezene. Journal of the American Chemical
Society, 77, 3233–3237, 1955.
201. Gatto, V.J., W.E. Moehle, T.W. Cobb, and E.R. Schneller. Oxidation fundamentals and its application
to turbine oil testing. Presented at the ASTM Symposium on Oxidation and Testing of Turbine Oils,
December 5, 2005, Norfolk, VA.
202. Berger, H., T.A.B. Bolsman, and D.M. Brower. Catalytic inhibition of hydrocarbons autoxidation by
secondary amines and nitroxides. In Developments in Polymer Stabilisation, 6. G. Scott, ed., Elsevier
Applied Science Publishers, London, 1–27, 1983.
CRC_59645_Ch001.indd 48CRC_59645_Ch001.indd 48 12/4/2008 3:33:25 PM12/4/2008 3:33:25 PM
Antioxidants 49
203. Jensen, R.K., S. Korcek, M. Zinbo, and J.L. Gerlock. Regeneration of amines in catalytic inhibition
oxidation. Journal of Organic Chemistry, 60, 5396–5400, 1995.
204. Bridgewater, A.J. and M.D. Sexton. Mechanism of antioxidant action: reactions of alkyl and aryl sul-
phides with hydroperoxides. Journal of the Chemical Society, Perkin Trans. II, 530, 1978.
205. Scott, G. Synergism and antagonism, in Atmospheric Oxidation and Antioxidants. vol. 2, G. Scott, ed.,
Elsevier Science Publishers B.V., Amsterdam, 431–457, 1993.
206. Hsu, S.M. Review of laboratory bench tests in assessing the performance of automotive crankcase oils.
Lubrication Engineering, 37(12), 722–731, 1981.
207. Sharma, B.K. and A.J. Stipanovic. Development of a new oxidation stability test method for lubricating
oils using high-pressure differential scanning calorimetry. Thermochimica Acta, 402, 1–18, 2003.
208. Zhang, Y., P. Pei, J.M. Perez, and S.M. Hsu. A new method to evaluate deposit-forming tendency
of liquid lubricants by differential scanning calorimetry. Lubrication Engineering, 48(3), 189–195,
1992.
209. Hsu, S.M., A.L. Cummings, and D.B. Clark. Evaluation of automotive crankcase lubricants by differential
scanning calorimetry. SAE Technical Paper 821252, 1982.
210. CEC L-85-T-99. Hot surface oxidation — pressure differential scanning calorimeter (PDSC).
211. ASTM Standard D 6186-98. Standard test method for oxidation induction time of lubricating oils by
pressure differential scanning calorimetry (PDSC).
212. Adamczewska, J.Z. and C. Love. Oxidative stability of lubricants measured by PDSC CEC L-85-T-99
test procedure. Journal of Thermal Analysis and Calorimetry, 80, 753–759, 2005.
213. Adhvaryu, A., S.Z. Erhan, S.K. Sahoo, and I.D. Singh. Thermo-oxidative stability studies on some new
generation API group II and III base oils. Fuel, 81(6), 785–791, 2002.
214. Migdal, C.A. The in uence of hindered phenolic and aromatic amine antioxidants on the stability of
base oils. 213th ACS National Meeting Preprint, San Francisco, April 13–17, 1997.
215. Rohrbach, P., P.C. Hamblin, and M. Ribeaud. Bene ts of antioxidants in lubricants and greases assessed
by pressurized differential scanning calorimetry. Tribotest Journal, 11(3), 233–246, 2005.
216. Jain, M.R., R. Sawant, R.D.A. Paulmer, D. Ganguli, and G. Vasudev. Evaluation of thermo-oxidative
characteristics of gear oils by different techniques: effect of antioxidant chemistry. Thermochimica
Acta, 435(2), 172–175, 2005.
217. Nakanishi, H., K. Onodera, K. Inoue, Y. Yamada, and M Hirata. Oxidative stability of synthetic
lubricants. Lubrication Engineering, 53(5), 29–37, 1997.
218. Sharma, B.K., J.M. Perez, and S.Z. Erhan. Soybean oil-based lubricants: a search for synergistic
antioxidants. Energy & Fuels, 21, 2408–2414, 2007.
219. Cheenkachorn, K., J.M. Perez, and W.A. Lloyd. Use of pressurized differential scanning calorimetry
(PDSC) to evaluate effectiveness of additives in vegetable oil lubricants. ICE (American Society of
Mechanical Engineers), 40, 197–206, 2003.
220. Gamlin, C.D., N.K. Dutta, N.R. Choudhury, D. Kehoe, and J. Matisons. Evaluation of kinetic parameters
of thermal and oxidative decomposition of base oils by conventional, isothermal and modulated TGA
and pressure DSC. Thermochimica Acta, 392–393, 357–369, 2002.
221. Gatto, V.J., H.Y. Elnagar, W.E. Moehle, and E.R. Schneller. Redesigning alkylated diphenylamine
antioxidants for modern lubricants. Lubrication Science, 19(1), 25–40, 2007.
222. Florkowski, D.W. and T.W. Selby. The development of a thermo-oxidation engine oil simulation test
(TEOST), SAE Technical Paper 932837, 1993.
223. ASTM Standard D 6335-03b. Standard test method for determination of high temperature deposits by
thermal-oxidation engine oil simulation test.
224. Selby, T.W. and D.W. Florkowski. The development of the TEOST protocol MHT bench test of engine
oil piston deposit tendency. Presented at 12th Esslingen Colloquium, January 11–13, 2000, Esslingen,
Germany.
225. ASTM Standard D 7097-05. Standard test method for determination of moderately high temperature
piston deposits by thermal-oxidation engine oil simulation test — TEOST MHT.
226. Anonymous. Correlation of TEOST performance with molar soap concentration for optimal deposit
performance. Research Disclosure, 409, 531, 1998.
227. Sun, J.X., P.T. Pei, Z.S. HU, and S.M. Hsu. A modi ed thin- lm oxygen update test (TFOUT) for
lubricant oxidative stability study. Lubrication Engineering, May, 12–19, 1998.
228. ASTM Standard D 4702-02a, Standard test method for oxidation stability of gasoline automotive engine
oils by thin- lm oxygen uptake (TFOUT).
CRC_59645_Ch001.indd 49CRC_59645_Ch001.indd 49 12/4/2008 3:33:26 PM12/4/2008 3:33:26 PM
50 Lubricant Additives: Chemistry and Applications
229. Ku, C.S. and S.M. Hsu. A thin- lm oxygen uptake test for the evaluation of automotive crankcase
lubricants. Lubrication Engineering, 40(2), 75–83, 1984.
230. ASTM Standard D 943-04a, Standard test method for oxidation characteristics of inhibited mineral oils.
231. ASTM Standard D 4310-03. Standard test method for determination of the sludging and corrosion
tendencies of inhibited mineral oils.
232. Yano, A., S. Watanabe, Y. Miyazaki, M. Tsuchiya, and Y. Yamamoto. Study on sludge formation during
the oxidation process of turbine oils. Tribology Transactions, 47, 111–122, 2004.
233. Cerny, J., D. Landtova, and G. Sebor. Development of a new laboratory oxidation test for engine oils.
Petroleum and Coal, 44(1–2), 48–50, 2002.
234. Cerny, J., Z. Strnad, and G. Sebor. Composition and oxidation stability of SAWE 15W-40 engine oils.
Tribology International, 34(2), 127–134, 2001.
235. IP 280/89. Determination of oxidation stability of inhibited mineral turbine oils, in standard methods
for analysis and testing of petroleum and related products. The Institute of Petroleum, 1994.
236. Jayaprakash, K.C., S.P. Srivastava, K.S. Anand, and K. Goel. Oxidation stability of steam turbine oils
and laboratory methods of evaluation. Lubrication Engineering, 49(2), 89–95, 1984.
237. ASTM Standard D 2272-02. Standard test method for oxidation stability of steam turbine oils by
rotating pressure vessel.
238. Swift, S.T., K.D. Butler, and W. Dewald. Turbine oil quality and eld application requirements,
in Turbine Lubrication in the 21st Century, ASTM STP 1407, W.R. Herguth and T.M. Warne, eds.,
American Society for Testing and Materials, West Conshohocken, PA, 2001.
239. Mookken, R.T., D. Saxena, B. Basu, S. Satapathy, S.P. Srivastava, and A.K. Bhatnagar. Dependence of
oxidation stability of steam turbine oil on base oil composition. Lubrication Engineering, 53(10), 19–24,
1997.
240. Gatto, V.J. and W.E. Moehle. Lubricating oil composition with reduced phosphorus levels. U.S. Patent
Application 2006/0223724 A1 (October 5, 2006, Albemarle Corporation).
241. Gatto, V.J. and M.A. Grina. Effects of base oil type, oxidation test conditions and phenolic antioxidant
structure on the detection and magnitude of hindered phenol/diphenylamine synergism. Lubrication
Engineering, 55(1), 11–20, 1999.
242. Dong, J. and C.A. Migdal. Lubricant compositions stabilized with multiple antioxidants. U.S. Patent
Application 2006/0128574 A1 (June 15, 2006, Crompton Corporation).
243. Niu, Q.S., H. Chui, and L.P. Yang. Effects of lube base oil composition on the lubricant oxidation.
Shiyou Xuebao Shiyou Jiagong, 2(2), 61, 1986.
244. Adhvaryu, A., Y.K. Sharma, and I.D. Singh. Studies on the oxidative behavior of base oils and their
chromatographic fractions. Fuel, 78, 1293, 1999.
245. Hsu, S.M., C.S. Ku, and R.S. Lin. Relationship between lubricating basestock composition and the
effects of additives on oxidation stability. SAE Technical Paper 821237, 1982.
246. Adhvaryu, A., S.Z. Erhan, Z.S. Liu, and J.M. Perez. Oxidation kinetic studies of oils derived from
unmodi ed and genetically modi ed vegetables using pressurized differential scanning calorimetry
and nuclear magnetic resonance spectroscopy. Thermochim Acta, 364, 87–97, 2000.
247. Stunenburg, F., A. Boffa, R. van den Bulk, K. Narasaki, M. Cooper, and G. Parsons. Impact of biodiesel
use on the lubrication of diesel engines. Presented at the 13th Annual Fuels and Lubes Asia Conference.
Bangkok, Thailand, March 7–9, 2007.
CRC_59645_Ch001.indd 50CRC_59645_Ch001.indd 50 12/4/2008 3:33:26 PM12/4/2008 3:33:26 PM
51
2
Zinc Dithiophosphates
Randolf A. McDonald
CONTENTS
2.1 Introduction ............................................................................................................................. 51
2.2 Synthesis and Manufacture ..................................................................................................... 51
2.3 Chemical and Physical Nature ................................................................................................ 52
2.4 Thermal and Hydrolytic Stability ...........................................................................................53
2.5 Oxidation Inhibition ...............................................................................................................56
2.6 Antiwear and Extreme-Pressure Film Formation ................................................................... 58
2.7 Applications ............................................................................................................................59
References ........................................................................................................................................ 61
2.1 INTRODUCTION
Zinc dialkyldithiophosphates (ZDDPs) have been used for more than 50 years in the lubricant
industry as low-cost, multifunctional additives in engine oils, transmission uids, hydraulic uids,
gear oils, greases, and other lubricant applications. The power of this particular compound is in
its ability to simultaneously function as an excellent antiwear agent, a mild extreme-pressure (EP)
agent, and an effective oxidation and corrosion inhibitor, all at a very low cost in comparison with
the alternate chemistries available in the market. This is why it is still manufactured on a large
scale by companies such as the ExxonMobil Corporation, Chevron Corporation, Ethyl Corporation,
Lubrizol Corporation, and others. To date, as much as 300 million lb of ZDDP is still manufac-
tured annually in the industrialized West.
2.2 SYNTHESIS AND MANUFACTURE
ZDDP was rst patented on December 5, 1944, by Herbert C. Freuler of the Union Oil Company of
California in Los Angeles [1]. The multifunctionality of ZDDP was immediately noticed as Freuler
indicated a noticeable increase in both the oxidation and the corrosion resistance of the lubricants
tested with the novel compound at a 0.1–1.0% treatment level. The initial synthesis Freuler carried
out involved the reaction of 4 mol of the intermediate dialkyldithiophosphate acid and 1 mol of
hydrogen sul de
4 ROH + P
2
S
5
2(RO)
2
P SH + H
2
S
S
→
(2.1)
followed by neutralization of the acid with 1 mol of zinc oxide
2(RO)
2
P SH + ZnO → 2(RO)
2
P SZnS P(OR)
2
+ H
2
O
S
S S
(2.2)
CRC_59645_Ch002.indd 51CRC_59645_Ch002.indd 51 3/20/2009 5:33:52 PM3/20/2009 5:33:52 PM
52 Lubricant Additives: Chemistry and Applications
This synthetic route is still used today in the manufacturing of ZDDP. The P
2
S
5
, a ammable solid
produced from the high-temperature reaction between elemental sulfur and phosphorus, is provided
to the ZDDP manufacture in sealed aluminum bins containing 500–7200 lb P
2
S
5
. The P
2
S
5
is hop-
pered into the reactor containing alcohol under a blanket of nitrogen. This is due to the ignitability
of both the alcohol and the P
2
S
5
when exposed to air. The hydrogen sul de by-product, a highly
toxic gas, is either converted to sodium sul de solution in a caustic scrubber or thermally oxidized
to sulfur dioxide. The heat of reaction and rate of hydrogen sul de evolution are controlled by the
addition rate of the P
2
S
3
as well as the ow rate of the cooling water. The acid is then neutralized
by zinc oxide; the reaction temperature is controlled by the addition rate of reaction depending on
whether it is an acid to oxide or oxide to acid, addition scheme. Enough zinc oxide is used to neu-
tralize the acid to a pH range, which will give a product suitably stable to thermal degradation and
hydrogen sul de evolution. The water formed from the reaction and the residual alcohol is vacuum-
distilled. Any unreacted zinc oxide is then ltered, requiring a ltration system capable of removing
particles as small as 0.1–0.8 μm. A larger molar excess of zinc oxide is often necessary to obtain the
pH required for stability. The various manufactures have done much work to reduce the amount of
zinc oxide used to obtain product stability (such as the addition of low-molecular-weight alcohols or
carboxylic acids to lower the amount of residual sediment in the product before ltration) [2]. The
ltered liquid product, with or without additional petroleum oil, is then provided to the customer in
drums or in bulk.
2.3 CHEMICAL AND PHYSICAL NATURE
ZDDP is an organometallic compound having four sulfur atoms coordinated to the zinc atom,
which is in a tetrahedral, sp
3
hybridized state. A Raman spectrum of ZDDP shows a strong P–S
symmetric stretching band near 540 cm
–1
and the absence of a strong Raman band near 660 cm
–1
,
indicating a symmetrical sulfur–zinc coordination arrangement as in the following structure
RO
O
R
O
R
RO
P
P
S
S
S
S
Zn
(2.3)
versus structure 2.4
RO
OR
OR
RO
PP
S
SS
S
Zn
(2.4)
often given in the literature. The strong IR band at 600 cm
–1
pointing to P=S stretching would be
more consistent with PS
2
antisymmetrical stretching in light of the Raman spectrum [3]. The neu-
tral ZDDP molecules as represented in structure 3.1 actually exist as monomer, dimer, trimer, or
oligomer depending on the state of the ZDDP, crystalline or liquid, the concentration of ZDDP in
solvent, and the presence of additional compounds. The proposed structure for a tetramer in the case
of a neutral zinc diisobutyldithiophosphate in hexane as determined by dynamic light scattering is
shown in the following structure [4]:
RO
RO
RO
RO
RO
P
S
S
S
S
S
S
S
P
P
S
S
S
S
S
S
P
P
P
S
P
P
S
Zn
Zn
Zn
Zn
S
RO
RO
RO
OR
OR
OR
OR
OR
OR
O
R
OR
(2.5)
CRC_59645_Ch002.indd 52CRC_59645_Ch002.indd 52 3/20/2009 5:33:54 PM3/20/2009 5:33:54 PM
Zinc Dithiophosphates 53
Under overbased condition, when the ratio of dialkyldithiophosphate acid to zinc oxide is less than
2:1, a basic zinc salt
Zn
4
O(RO)
2
PS
6
S
(2.6)
will be synthesized along with the neutral salt. The basic salt is a tetrahedron of zinc atoms
surrounding a central oxygen atom with (RO)
2
PS
2
ligands along each edge of the tetrahedron.
Crystallographic analysis of pure basic zinc salts has established the near equivalency of P–S–Zn
bonds. Raman spectra have also shown symmetrical P–S stretching, supporting a symmetrical
sulfur–zinc coordination arrangement for the basic ZDDPs [3]. In the presence of water, as one
would encounter during commercial ZDDP manufacture, the basic zinc salt will be in equilibrium
with the basic zinc double salt as seen in the following reaction:
H
2
OZn
4
OZn
2
OH
(RO)
2
PS
6
S
+
2
3
R = alk
y
l,
p
hen
y
l, or alk
y
l
p
hen
y
l
(RO)
2
PS
S
(2.7)
The stoichiometric excess of zinc oxide used in commercial ZDDP manufacture gives rise to a
mixture of basic zinc salt (or zinc double salt) and neutral salt, the ratio depending on the amount
of excess zinc oxide used and the molecular weight of the alkyl groups involved, where short alkyl
groups tend to promote the formation
ZnOZn3
2
+
R = alkyl, phenyl, or alkylphenyl
Zn
4
O
(RO)
2
PS
S
(RO)
2
PS
S
(2.8)
but performance differences seen between the two salts with respect to wear would imply that a
more complex situation may exist [5]. As reported in the literature, basic ZDDP salts spontaneously
decompose in solution into neutral complexes and zinc oxide when the temperature is increased [6].
Pure ZDDPs, with alkyl groups of four carbons or less, are solid at ambient temperatures (with
the exception of sec-butyl, which is a semisolid at room temperature) and tend to have limited
or no solubility in petroleum base stocks. ZDDPs with aryl or alkyl groups with more than ve
carbons are liquid at ambient temperature. To utilize the less-expensive and more readily available
low-molecular-weight alcohols and yet to produce oil-soluble products, commercial manufactures
use mixtures of high- (i.e., more than four carbons) and low-molecular-weight alcohols to obtain a
statistical distribution of products favoring lesser amounts of pure low-molecular-weight ZDDPs.
Other methods have also been developed to increase the amount of lower- molecular-weight alco-
hols in ZDDPs. These include the addition of ammonium carboxylates to inhibit precipitation [7]
and the use of alkyl succinimides as solubilizing-complexing agents [8].
2.4 THERMAL AND HYDROLYTIC STABILITY
The study of the thermal degradation of ZDDP is important in that much of the tribologi-
cal characteristics of ZDDP can be explained by the effects of its decomposition products. The
thermal decomposition of ZDDP in mineral oil has been found to be extremely complex. ZDDP in
oil, upon heating to degradation, will give off volatile compounds such as ole n, alkyl disul de,
CRC_59645_Ch002.indd 53CRC_59645_Ch002.indd 53 3/20/2009 5:33:54 PM3/20/2009 5:33:54 PM