Rudnick L. Lubricant Additives: Chemistry and Applications (Присадки, добавки к смазкам)
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114 Lubricant Additives: Chemistry and Applications
can be found within the same molecule. Their advantageous physical properties—for example, low
color and odor and good solubility for other additives—make them attractive components for addi-
tive packages. However, although the future looks bright in industrial oil applications in view of
current pressure on sulfur and chlorine (mainly as a result of environmental concerns), the potential
in automotive engine oil remains uncertain due to the current downward pressure on phosphorus.
In fuels, the question is whether the reduced level of sulfur will require replacement by other AW
additives and, if so, whether phosphorus can be incorporated without adversely affecting other
properties (e.g., catalyst ef ciency).
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APPENDIX A: EARLY PATENT LITERATURE ON PHOSPHORUS-
CONTAINING COMPOUNDS
N
EUTRAL PHOSPHATES
U.S. Patent 2,723,237, Texas Oil Co.
NEUTRAL PHOSPHITES
As AW/EP Additives
British Patent 1,052,751, British Petroleum (chlorethyl phosphite and a chlorparaf n)
British Patent 1,164,565, Mobil Oil Corp. (alkyl or alkenyl phosphite and a fatty acid ester)
British Patent 1,224,060, Esso Research and Engineering Co.
U.S. Patent 2,325,076, Atlantic Re ning Co.
U.S. Patent 2,758,091, Shell Development Co. (haloalkyl or haloalkarylphosphites)
U.S. Patent 3,318,810, Gulf Research & Development Co. (phosphites and molybdenum compounds)
As Antioxidants
U.S. Patent 2,326,140, Atlantic Re ning Co.
U.S. Patent 2,796,400, C.C. Wake eld & Co.
ACID PHOSPHATES/PHOSPHITES
British Patent 1,105,965, British Petroleum Co Ltd. (acid hydrocarbyl phosphite and phosphates or thiophos-
phates or phosphoramidates)
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Ashless Phosphorus-Containing Lubricating Oil Additives 119
British Patent 1,153,161, Nippon Oil Co.
U.S. Patent 2,005,619, E. I. du Pont de Nemours
U.S. Patent 2,642,722, Tide Water Oil Co.
French Patent 797,449, E.I. du Pont de Nemours
PHOSPHONATES
British Patent 823,008, Esso Research and Engineering Co. (dicarboxylic acid and either a haloalkane phos-
phonate, a haloalkyl phosphate or phosphite and optionally a neutral alkyl or aryl phosphate)
British Patent 884,697, Shell Research Ltd. (dialkenyl phosphonates)
British Patent 899,101, British Petroleum Co. (amino phosphonates)
British Patent 993,741, Rohm and Haas Co. (aminoalkane phosphonates)
British Patent 1,083,313, British Petroleum Co. (amino phosphonates)
British Patent 1,247,541, Mobil Oil Corp. (Dialkyl-n-alkylphosphonate or alkylammonium salts of
dialkylphosphonates)
U.S. Patent 2,996,452, US Sec of Army (di-(2-ethylhexyl) lauroxyethyl phosphonate)
U.S. Patent 3,329,742, Mobil Oil Corp. (diaryl phosphonates)
U.S. Patent 3,600,470, Swift & Co. (hydroxy or alkoxy phosphonates and their amine salts)
U.S. Patent 3,696,036, Mobil Oil Corp. (tetraoctyl-(dimethylamino) methylene diphosphonate)
U.S. Patent 3,702,824, Texaco Inc. (hydroxyalkylalkane phosphonate)
ALKYL- AND ARYLPOLYETHYLENEOXY-PHOSPHORUS COMPOUNDS
U.S. Patent 2,372,244, Standard Oil Dev. Co.
AMINE SALTS
British Patent 705,308, Bataafsche Petroleum Maatschappij (substituted monobasic phosphonic acid and
amine salts thereof)
British Patent 978,354, Shell International Research (alkali metal-amine salt of a halohydrocarbyl phosphonic
acid)
British Patent 1,002,718, Shell International Research (alkylamine salt of diaryl acid phosphate)
British Patent 1,199,015, British Petroleum Co. Ltd. (quaternary ammonium salts of dialkyl phosphates)
British Patent 1,230,045, Esso Research and Engineering Co. (quaternary ammonium salts of alkyl phos-
phonic and phosphonic acids)
British Patent 1,266,214, Esso Research and Engineering Co. (neutral phosphate and a neutral alkylamine
hydrocarbyl phosphate)
British Patent 1,302,894, Castrol Ltd. (tertiary amine phosphonates)
British Patent 1,331,647, Esso Research and Engineering Co. (quaternary ammonium phosphonates)
U.S. Patent 1,936,533, E. I. du Pont de Nemours. (triethanolamine salts)
U.S. Patent 3,553,131, Mobil Oil Corp. (tertiary amine phosphonate salts)
U.S. Patent 3,668,237, Universal Oil Products Co. (tertiary amine salts of polycarboxylic acid esters of
bis(hydroxyalkyl)-phosphinic acid)
PHYSICAL MIXTURES OF PHOSPHORUS AND SULFUR AND CHLORINE COMPOUNDS
British Patent 706,566, Bataafsche Petroleum Maatschappij (a phosphorus compound, e.g., a trialkyl phos-
phate, a glycidyl either and a disulphide)
British Patent 797,166, Esso Research and Engineering Co. (TCP and a metal soap of a sulphonic acid)
British Patent 841,788, C.C. Wake eld & Co. Ltd. (chlorinated hydrocarbon, a disulphide, and a dialkyl
phosphite)
British Patent 967,760, The Distillers Co. Ltd. (disulphides, chlorinated wax, and a haloalkyl ester of an oxy-
acid of phosphorus)
British Patent 872,899, Esso Research and Engineering Co. (trialkyl phosphates and chlorinated benzene)
British Patent 1,222,320, Mobil Oil Corp. (diorganophosphonate and a sulphurized hydrocarbon or sulphu-
rized fat)
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120 Lubricant Additives: Chemistry and Applications
British Patent 1,287,647, Stauffer Chemical Co. (phosphonates or halogenated alkylphosphates, sulphurised
oleic acid, and sebacic acid)
British Patent 1,133,692, Shell International (TCP and triphenylphosphorothionate)
British Patent 1,162,443, Mobil Oil Corp. (neutral or acid, alkyl or alkenyl phosphite, and a sulphurized poly-
isobutylene, triisobutylene, or a sulphurized dipentene)
U.S. Patent 2,494,332, Standard Oil Dev. Co. (thiophosphates and TCP)
U.S. Patent 2,498,628, Standard Oil Dev. Co. (sulfurized/phosphorized fatty material and TCP or tricresyl
phosphite)
U.S. Patent 3,583,915, Mobil Oil Corp. (di(organo)phosphonate, and an organic sulphur compound selected
from sulphurized oils and fats, a sulphurized monoole n or an alkyl polysulphide)
MISCELLANEOUS PHOSPHORUS COMPOUNDS
British Patent 1,035,984, Shell Research Ltd. (diaryl chloralkyl phosphate or thiophosphate)
British Patent 1,193,631, Albright & Wilson Ltd. (hydroxyalkyl disphosphonic acid/alkylene oxide reaction
products)
British Patent 1,252,790, Shell International Research (pyrophosphonic and pyrophosphinic acids and their
amine salts)
U.S. Patent 3,243,370, Monsanto Co. (phosphinylhydrocarbyloxy phosphorus esters)
U.S. Patent 3,318,811, Shell Oil Co. (diacid diphosphate ester)
U.S. Patent 3,640,857, Dow Chemical Co. (tetrahaloethyl phosphates)
APPENDIX B: ADDITIONAL LITERATURE AND PATENT REFERENCES
ON THE MECHANISM AND PERFORMANCE OF
PHOSPHORUS-CONTAINING ADDITIVES
N
EUTRAL PHOSPHATES
Garaud, Y., M.D. Tran. Photoelectron spectroscopy investigation of tricresyl phosphate anti-wear action.
Analusis 9(5): 231–235, 1981.
Ghose, H.M., J. Ferrante, F.C. Honecy. The effect of tricresyl phosphate as an additive on the wear of iron.
NASA Tech. Memo, NASA-TM-100103, E-2883, NASI. 15: 100103.
Han, D.H., M. Masuko. Comparison of antiwear additive response among several base oils of different polari-
ties. Tribol Trans 42(4): 902–906, 1999.
Han, D.H., M. Masuko. Elucidation of the antiwear performance of several organic phosphates used with dif-
ferent polyol esters base oils from the aspect of interaction between the additive and the base oil. Tribol
Trans 41(4): 600–604, 1998.
Kawamura, M., K. Fujito. Organic sulfur and phosphorus compounds as extreme pressure additives. Wear
72(1): 45–53, 1981.
Koch, B., E. Jantzen, V. Buck. Properties and mechanism of action of organism phosphoric esters as antiwear
additives in aviation. Proc 5th Int Tribol Coll Esslingen, Ger Vol. 1, 3/11/1–3/11/12, 1986.
Morimoto, T. Effect of phosphate on the wear of silicon nitride sliding against bearing steel. Wear 169(2):
127–134, 1993.
Perez, J.M. et al. Characterization of tricresyl phosphate lubricating lms. Tribol Trans 33(1): 131–139,
1990.
Riga, A., J. Cahoon, W.R. Pistillo. Organophosphorus chemistry structure and performance relationships in
FZG gear tests. Tribol Lett 9(3,4): 219–225, 2001.
Riga, A., W.R. Pistillo. Surface and solution properties of organophosphorus chemicals and performance
relationships in wear tests. Proc 27th NATAS Ann Conf Therm Anal Appl 708–713, 1999.
Ren, D., A.J. Gelman. Reaction mechanisms in organophosphate vapor-phase lubrication of metal surfaces.
Tribol Int 34(5): 353–365, 2001.
Weber, K., E. Eberhardt, G. Keil. In uence of the chemical structure of phosphoric EP-additives on its effec-
tiveness. Schmierungstechnik 3(12): 372–377, 1972.
Wiegand, H., E. Broszeit. Mechanism of additive action. Model investigations with tricresyl phosphate. Wear
21(2): 289–302, 1972.
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Ashless Phosphorus-Containing Lubricating Oil Additives 121
Yamamoto, Y., F. Hirano. Effect of different phosphate esters on frictional characteristics. Tribol Int 13(4):
165–169, 1980.
Yamamoto, Y., F. Hirano. The effect of the addition of phosphate esters to paraf nic base oils on their lubri-
cating performance under sliding conditions. Wear 78(3): 285–296, 1982.
Yanshang, Ma., et al. The effect of oxy-nitrided steel surface on improving the lubricating performance of
tricresyl phosphate. Wear 210(1–2): 287–290, 1997.
NEUTRAL PHOSPHITES
Barabanova, G.V. et al. Effect of phosphoric, thiophosphoric and phosphorus acid neutral ester-type additives
on the lubricating capacity of C5-C9 synthetic fatty acid pentaerythritol ester. Pererabotke Nefti 17:
57–61, 1976.
Orudzheva, I.M. et al. Synthesis and study of some aryl phosphites. 3rd Tekh Konf Neftekhim 3: 411–415,
1974.
Sanin, P.I. et al. Tr Inst Nefti Akad Nauk SSSR, 14: 98, 1960.
Sanin, P.I., A.V. Ul’yanova. Prisadki Maslam Toplivam, Trudy Naucha. Tekhn Soveshch 189, 1960.
Wan, Y., Q. Xue. Effect of phosphorus-containing additives on the wear of aluminum in the lubricated aluminum-
on-steel contact. Tribol Lett 2(1): 37–45, 1996.
U.S. Patent 3,115,463/4.
U.S. Patent 3,652,411.
U.S. Patent 4,374,219.
ALKOXYLATED PHOSPHATES
Jia, X., X. Zhang. Antiwear property of water-soluble compound phosphate ester. Runhua Yu Mifeng 4
(25–25): 67, 1999.Wang, R. Study on water-soluble EP additives. Runhua Yu Mifeng 3(17–18): 51, 1994.
Zhang, X., X. Jia. Water soluble phosphate esters. Hebei Ligong Xueyuan Xuebao 21(2): 58–61, 1999.
AMINE SALTS
Forbes, E.S. et al. The effect of chemical structure on the load carrying properties of amine phosphates. Wear
18: 269, 1971.
Shi, H. Development trend of phosphorus-nitrogen-type extreme-pressure antiwear agents. Gaoqiao Shi 12(3):
37–41, 1997.
DIALKYL ALKYL PHOSPHONATES
Cann, P.M.E., G.J. Johnston, H.A. Spikes. The formation of thick lms by phosphorus-based antiwear addi-
tives. Proc Inst Mech Eng, I. Mech. E. Conf 543–554, 1987.
Dickert, J.J., C.N. Rowe. Novel lubrication properties of gold O, O-dialkylphosphorodithioates and metal
organophosphonates. ASLE Trans 20(2): 143–151, 1977.
Gadirov, A.A., A.K. Kyazin-Zade. Diphenyl esters of alpha-aminophosphonic acids as antioxidant and anti-
wear additives. Khim Tekhnol Topl Masel 3: 23–24, 1990.
Lashkhi, V.L. et al. Antiwear action of organophosphorus and chloroorganophosphorus compounds in lubri-
cating oils. Khim Tekhnol Topl Masel 2: 47–50, 1975.
Lashkhi, V.L. et al. IR spectroscopic study of phosphonic acid ester-antiwear additives for oil. Khim Tekhnol
Topl Masel 5: 59–61, 1977.
Lozovoi, Y., P.I. Sanin. Mechanism of action of phosphorus acid ester-type extreme pressure additives. IZV
Khim 19(1): 49–57, 1986.
Tang, J., Q. Cang, X. Zong. Preparation of phosphorus friction modi ers used in automatic transmissions
uids. Shiyou Lianzhi Yu Huagong 31(3): 17–20, 2000.
Wan, G.T.Y. The performance of one organic phosphonate additive in rolling contact fatigue. Wear 155(2):
381–387.
Xiong, R.-G., W. Hong, J.-L. Zuo, C.-M. Liu, X.-Z. You, J.-X. Dong, Z. Pei. Antiwear and extreme pres-
sure action of a copper (II) complex with alkyl phosphonic monoalkyl ester. J Tribol 118(3): 676–680,
1996.
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122 Lubricant Additives: Chemistry and Applications
MIXTURES OF PHOSPHORUS AND SULFUR COMPOUNDS
Kawamura, M. et al. Interaction between sulfur type and phosphorus type EP additives and its effect on lubri-
cating performance. Junkatsu 30(9): 665–670.
Kubo, K., Y. Shimakawa, M. Kibukawa. Study on the load-carrying mechanism of sulfur-phosphorus type
lubricants. Proc JSLE Int Tribol Conf 3: 661–666, 1985.
PCT Int Appl. WO 2002053687A2 (Shell Int Res).
Qiao, Y., B. Xu, S. Ma, X. Fang, Q. Xue. Study in synergistic effect mechanism of some extreme pressure and
antiwear additives in lubricating oil. Shiyou Xuebao, Shiyou Jiagong 13(3): 33–39, 1997.
Qiao, Y., X. Fang, H. Dang. Synergistic effect mechanism of the combination system of two typical additives
containing sulfur and phosphorus in lubricating oil. Mocaxue Xuebao 15(1): 29–38, 1995.
Xia, H. A study of the antiwear behaviour of S-P type gear oil additives in four-ball and Falex machines. Wear
112(3–4): 335–361, 1986.
GENERAL REFERENCES
Hartley, R.J., A.G. Papay. Function of additives. Antiwear and extreme pressure additives. Toraiborojisuto
40(4): 326–331, 1995.
Palacios, J.M. The performance of some antiwear additives and interference with other additives. Lubr Sci
4(3): 201–209, 1992.
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123
4
Detergents
Syed Q. A. Rizvi
CONTENTS
4.1 Introduction ...........................................................................................................................123
4.2 Detergent Types ....................................................................................................................125
4.3 Detergent Parameters ............................................................................................................ 125
4.4 Detergent Substrates..............................................................................................................127
4.5 Synthesis of Neutral and Basic Detergents ...........................................................................130
4.6 Testing ................................................................................................................................... 135
References ...................................................................................................................................... 139
4.1 INTRODUCTION
Modern equipment must be lubricated to prolong its lifetime. A lubricant* performs a number
of critical functions. These include lubrication, cooling, cleaning and suspending, and protecting
metal surfaces against corrosive damage [1]. Lubricant comprises a base uid and an additive pack-
age. The primary function of the base uid is to lubricate and act as a carrier of additives. The func-
tion of additives is either to enhance an already-existing property of the base uid or to add a new
property. The examples of already-existing properties include viscosity, viscosity index, pour point,
and oxidation resistance. The examples of new properties include cleaning and suspending ability,
antiwear performance, and corrosion control. The extent of the desirability of various properties
differs from lubricant to lubricant and largely depends on the conditions of use. Automotive use,
for example, requires lubricants with good oxidation resistance, suitable low- and high-temperature
viscosities, high-viscosity index (i.e., minimum loss in viscosity with an increase in temperature),
and good cleaning and suspending ability. Conversely, the use as nonautomotive lubricants, such
as industrial and metalworking lubricants, emphasizes oxidation resistance, antiwear performance,
corrosion control, and cooling ability.
One of the most critical properties of the automotive lubricants, especially engine oils, is their
ability to suspend undesirable products from thermal and oxidative degradation of the lubricant.
Such products form when the by-products of fuel combustion, such as hydroperoxides and free radi-
cals, go past piston rings into the lubricant and, being reactive species, initiate lubricant oxidation.
The resulting oxidation products are thermally labile and decompose to highly polar materials with
a tendency to separate from the bulk lubricant and form surface deposits and clog small openings.
The former will lead to malfunctioning of the closely tted surfaces, such as those between pistons
and cylinder walls, and the latter will impair oil ow to parts needing lubrication. The separation
tendency of these products relates to their high polar to nonpoplar ratio [2], which makes them less
soluble in largely nonpolar base oil. A lubricant with high-oxidation resistance, due to the quality
of the base uid or the presence of a good oxidation inhibitor additive package, will slow down the
formation of these undesirables.
* The terms “lubricant” and “oil” are interchangeable and are different from the terms “base oil” and “base uid.” Lubri-
cant and oil imply base oil or a base uid plus additives.
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