US3361668A - Lubricating compositions containing light-colored and improved group ii metal phosphorodithioates - Google Patents

Lubricating compositions containing light-colored and improved group ii metal phosphorodithioates Download PDF

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US3361668A
US3361668A US498107A US49810765A US3361668A US 3361668 A US3361668 A US 3361668A US 498107 A US498107 A US 498107A US 49810765 A US49810765 A US 49810765A US 3361668 A US3361668 A US 3361668A
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phosphorodithioic acid
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diester
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Herbert F Wiese
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Lubrizol Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids

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  • This invention relates to a process for preparing light colored and relatively non-corrosive, oil-soluble 0,0- phosphorodithioic acid diesters and metal salts prepared from such 0,0'-phosphorodithioic acid diesters, particularly the zinc salts.
  • the zinc salts of 0,0-phosphorodithioic acid diesters have long been known to have useful properties as inhibitors of corrosion and oxidation.
  • The are especially useful as additives for crankcase lubricants in internal combustion engines in which service they provide a means of combatting deterioration of the oil and prevent corrosion of the relatively moving surfaces, particularly the bearing surfaces. Their use for such purposes is well established and their usefulness in this capacity has increased with the development and refinement of the modern internal combustion engine.
  • 0,0'-phosphorodithioic acid diesters are manufactured by reacting about 4 equivalents of an organic monohydroxy compound, e.g., an alcohol or a phenol with one mole of phosphorus pentasulfide at temperatures of from about 50 C. to about 150 C. with the evolution of hydrogen sulfide as illustrated by the following equation:
  • the oil-soluble metal phosphorodithioate diester salts are usually manufactured by neutralizing the phosphorodithioic acid diester with a basically reacting metal compound, preferably the oxide, frequently With a small amount of water added, at temperatures of from about 50 to about 150 C.
  • a phosphorodithioic acid diester is usually assumed to have the structure shown in the above equation wherein the thiol group attached to the phosphorus atom accounts for its relatively strong acidic character.
  • the alcohols used are anhydrous, traces of water which are present in the reaction mixture react with the phosphorus pentasulfide causing the formation of small amounts of monesters of phosphorodithioic acid or phosphoromonothioic acid and even some unesterified phosphorus and sulfur containing acids, which may also contribute to their strongly acidic character.
  • the commercially prepared phosphorodithioic acid diesters are sufiiciently strong acids to be corrosive to metals and the use of special corrosion resistant equipment is generally required in their manufacture and storage. Therefore, the phosphorodithioic acid diesters usually are manufactured in stainless steel or glass lined steel equipment and it is standard practice to store them in stainless steel storage bins.
  • An object of this invention is to provide a process for preparing 0,0'-diesters of phosphorodithioic acid which are less corrosive to metals.
  • Another object of this invention is to provide a process for preparing light colored 0,0-diesters of phosphorodithioic acid.
  • Another object is to provide a process for preparing light colored metal salts of 0,0'-diesters of phosphorodithioic acids.
  • Still another object of this invention is to provide a process for preparing light colored zinc salts of 0,0-di esters of phosphorodithioic acid.
  • a process for preparing improved 0,0'-diesters of phosophorodithioic acid comprising reacting at from about 20 C. to about 200 C., one mole of phosphorus pentasulfide with about 4 equivalents of a mixture of from about to about 99.95% by weight of a monohydroxy organic compound selected from the class consisting of alcohols and phenols and from about 0.05% to about 5% by Weight of an amine selected from the class consisting of alkyl amines, cycloalkyl amines and heterocyclic amines.
  • a process for preparing improved 0,0-diesters of phosophorodithioic acid comprising reacting from about 95% to about 99.95% by weight of an 0,0-diester of phosphorodithioic acid with from about 0.05% to about 5% by Weight of an amine selected from the class consisting of alkyl amines, cycloalkyl amines and heterocyclic amines.
  • Light coiored phosphorodithioic acid diesters are obtained by the process of this invention in one of two ways. Either a small amount of a suitable amine is added to the alcohol before the alcohol is reacted with phosphorus pentasulfide or the phosphorodithioic acid diester is first prepared and a small amount of a suitable amine is then added. In either case, the product obtained is appreciably lighter in color than that made by prior art processes without the use of an amine.
  • t is preferred to mix the amine with the alcohol before reaction with phosphorus pentasulfide in order to take advantage of the reduced corrosiveness of the acid toward the processing equipment during the acid formation.
  • the improved phosphorodithioic acid diesters are prepared by reacting a mixture of an alcohol or phenol and an amine with phosphorus pentasulfide
  • the mixture may contain from about 95 to 99.95% (by weight) of alcohol or phenol and from about 0.05% to 5% of the amine.
  • the ratio of alcohol-amine mixture to phosphorus pentasulfide is about 4 equivalents per mole but an excess of the alcohol or phenol may be used as a solvent for the reaction or an excess of phosphorus pentasulfide may be used if it is desirable to completely consume the alcohol. In the latter case, the excess phosphorus pentasulfide is removed by suitable means such as littering or centrifuging.
  • four equivalents of alcohol-amine mixture is reacted with about one mole or slightly more than one mole of phosphorus pentasulfide.
  • the number of equivalents of the alcohol-amine mixture is their combined number of equivalents. Since the alcohols or phenols preferred in the process are monohydric alcohols, the equivalent Weight of such alcohol or phenol is its molecular weight. The equivalent weight of the amine is its molecular weight divided by the number of nitrogen atoms in the molecule. Thus, a monoamine has one equivalent per mole, a diamine has two equivalents per mole, a triamine has three equivalents per mole, etc.
  • the acid forming reaction is usually carried out by the slow, continuous addition of phosphorus pentasulfide or by the addition of small, discrete increments of phosphorus pentasulfide to the alcohol-amine mixture.
  • the acid can also 'be manufactured in a continuous process such as that described in US. Patent No. 2,862,947 wherein both alcohol and P 3 are added continuously to a reaction zone and the acid product is continuously removed. Reaction may be effected :at temperatures of from about 20 to about 200 C. The preferred temperature range is from about 60 C. to about 130 C.
  • Suitable monohydroxy organic compounds useful in the preparation of the improved 0,0'-diesters of phosphorodithioic acid include alcohols, phenols, and alkyl phenols, including their substituted derivatives, e.g., nitro-, halo-, alkoxy-, hydroxy-, carboxy-, etc.
  • Suitable alcohols include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, Z-butanol, Z-methyl-propanol, n-pentanol, 2- pentanol, 3-pentanol, 2-methylbutanol, 3-methyl-2-pentanol, n-hexanol, 2-hexanol, 3-hexanol, Z-methyl-Z-pentanol, 4-methyl-3-pentanol, cyclohexanol, chlorocyclohexanol, methylcyclohexanol, heptanol, 2-ethylhexanol, n-octanol, 2,2-dimethyloctanol, nonanol, dodecanol, octadecanol, eicosanol, etc.
  • the phenols suitable for the purposes of this invention include alkyl phenols and substituted phenols, e.g., phenol, chlorophenol, bromophenol, nitrophenol, methoxyphenol, cresol, propylphenol, butylphenol, amylphenol, heptylphenol, octylphenol, nonylphenol, octadecylphenol, etc.
  • the monohydroxy organic compounds su-itable for purposes of this invention may have from 1 to about 30 carbon atoms.
  • a mixture of high molecular weight and low molecular weight alcohols may be used.
  • the use of mixtures of alcohols also enables the utilization of cheaper alcohols which by themselves do not yield oil-soluble phosphorodithioate acid salts.
  • a mixture of isopropyl and hexyl alcohols can be used to produce a very effective oil-soluble metal phosphorodithioate.
  • mixtures of simple acids, i.e., acids prepared from single alcohol can be reacted with the metal neutralizing agent to produce less expensive, oil-soluble metal salts.
  • the amines suitable for use in this invention for preparing the improved phosphorodithioic acid diester and their metal salts include the primary, secondary, and tertiary alkylamines and cycloalkylamines.
  • suitable amines include ethylamine, propylamine, isopropylarnine, butylarnine, isobutylamine, tertiary butylamine, n-pentylamine, isopentylamine, 3-methyl-2 butylamine, nhexylamine, Z-methylpentylamine, Z-ethylbutylamine, 2,2- dimethylbutylamine, n-heptylamine, Z-methylhexylamine, 3-methylhexylamine, 2-ethylpentylamine, n-octylamine, 2-ethylhexylamine, 2,2-dimethyldodecylamine, dimethylamine, diethylamine, dipropy
  • heterocyclic amines that is, amines in which the amino nitrogenatom is a part of a ring made up of dissimilar atoms such as carbon, oxygen and sulfur as well as nitrogen.
  • heterocyclic amines include pyrrole, dihydropyrrole, pyrrolidine, oxazolidine, isoxazolidine, thiazolidine, oxazidine, piperidine, piperazine, morpholine, 4-(Z-aminoethoxy)ethylmorpholine, 2-(4-morpholinylethoxy)ethanol, bis-2- (4-morpholinyl)ethyl ether,
  • the improved metal salts of 0,0-diesters of phosphorodithioic acid of this invention are preferably salts of metals in Group II of the Periodic Table and comprise the salts of calcium, barium, strontium, zinc, and cadmium.
  • the zinc and barium phosphorodithioate diesters are particularly effective as additives in lubricating compositions and are therefore preferred for use herein.
  • metal salts of the phosphorodithioic acid diesters are well-nown. They are prepared, for example, by the reaction of the acid with a metal neutralizing agent such as zinc, zinc oxide, or barium oxide. Simply mixing and heating these reactants is suflicient to cause the neutralization to take place and the resulting product is sufiiciently pure for the purpose of this invention.
  • a metal neutralizing agent such as zinc, zinc oxide, or barium oxide.
  • Example 1 A mixture of 381 parts (2.93 equivalents) of isooctanol and 4 parts (0.028 equivalent) of a heterocyclic amine mixture consisting essentially of 4-(2-aminoethoxy) ethylmorpholine, 2-(4-morpholinylethoxy)ethanol, and bis-2-(4-morpholinyl)ethy1 ether and having a nitrogen content of about 11% and an equivalent weight of about 142 is heated to 75 C. in one hour and 164 parts (0.74 mole) of phosphorus pentasulfide is added in one hour at 75-90 C. The reaction mixture is held at 100 C. for one hour and is filtered through a diatomaceous earth filter pad to obtain a clear, very light green liquid which is found to contain 17.37% sulfur, 8.05% phosphorus, 0.02% nitrogen.
  • a heterocyclic amine mixture consisting essentially of 4-(2-aminoethoxy) ethylmorpholine, 2-(4-morpholinyle
  • Example 2 A mixture of 1213 parts (16.4 equivalents) of isobutanol, 779 parts (8.83 equivalents) of primary amyl alcohol, and parts (0.67 equivalent) of the amine used in Example 1 is heated to 70 C. and 1368 parts (6.17 moles) of phosphorus pentasulfide is added at 7075 C. in 3 hours. The reaction mixture is heated for 1% hours at 7585 C. and filtered. The filtrate (3158 parts). is a clear, light green liquid containing 11.7% phosphorus, 24.8% sulfur, and 0.35% nitrogen.
  • Example 4 A mixture of 96 parts (1.3 equivalents) of isobutanol, 61.6 parts (0.70 equivalent) of a primary amyl alcohol, 1.6 parts (0.011 equivalent) of the amine used in Example l is heated to 70 C. and 111 parts (0.5 mole) of phosphorus pentasulfide is added at 70-75 C. in one hour. The reaction mixture is heated anadditional hour at 7S-85 C. and then filtered. The filtrate is the product;
  • Example 5 The process of Example 1 is repeated except that the quantity of iso-octa-nol used is 398 parts (3.06 equivalents), the quantity of amine used is 2 grams (0.014 equivalent), and the quantity of phosphorus pentasulfide is 171 parts (0.77 mole).
  • Example V A mixture of 204 parts (2 equivalents) of 3-methyl-2- pentanol and2 parts (0.23 equivalent) of amylarnine is heated to 80 C. and 111 parts (0.5 mole) of phosphorus pentasulfide is added at 8085 C. in one hour. The reaction mixture is heated for one hour at 90-95 C. and filtered. The filtrate is the product.
  • Example 7 To a mixture of 500 parts (2.6 equivalents) of heptylphenol and 25 parts (0.135 equivalent) of dodecylamine is added 155 parts (0.7 mole) of phosphorus pentasulfide at 75-85 C. in one hour. The reaction mixture is heated one hour at 100-105 C. and filtered. The filtrate is the product.
  • Example 8 A mixture of 245 parts (2.4 equivalents) of 3-methyl- 2-pentanol, 96 parts (1.6 equivalents) of isopropanol, and 3.4 parts (0.034 equivalent) of cyclohexylamine is heated to 70 C. and 222 parts (1.0 mole) of phosphorus pentasulfide is added in one hour. The mixture is held at 80- 90 C. for one hour and filtered. The filtrate is the product.
  • Example 9 Phosphorus pentasulfide, 112 parts (0.5 mole) is added to a mixture of 288 parts (2 equivalents) of nonyl alcohol and 2.9 parts (0.029 equivalent) of dipropylamine at 75- 85 C. in one hour and the reaction mixture is heated for one hour at 7585 C. before filtration.
  • Example 10 To 355 parts (1 equivalent) of diisooctyl phosphorodithioic acid, 3.6 parts (0.025 equivalent) of the amine mixture defined in Example 1 is added with stirring at 55 C. and held at 5055 C. for 3 hours. The product is a clear, light green liquid.
  • Example 11 Amylamine, 3.6 parts (0.04 equivalent) is added to diisooctyl phosphorodithioic acid, 355 parts (1 equivalent) at 24 C. The mixture is heated to 50 C. and held at that temperature for 3 hours. The product is a clear, light green liquid.
  • Example 12 The amine mixture defined in Example 1, 2.5 parts (0.018 equivalent) is added at ambient temperature to 252 parts (1 equivalent) of a dialkylphosphorodithioic acid made from a 65 mole percent isobutyl alcohol-35 mole percent primary amyl alcohol mixture. The mixture is heated to 50 C. and held at this temperature for 3 hours. The product is a clear, greenish liquid.
  • Example 13 Amylamine, 2.5 parts (0.029 equivalent) is added to 252 parts (1 equivalent) of the dialkylphosphorodithioic acid used in Example 12 at 24 C. The mixture is heated to 50 C. and held at that temperature for 3 hours. The product is a greenish, clear liquid.
  • Example 14 To 298 parts 1.0 equivalent) of di-4-methyl-2-pentyl phosphorodithioic acid, 3 parts (0.03 equivalent) of dipropylamine is added at 24 C. The mixture is heated to 50 C. and held at that temperature for 3 hours. The product is a clear, greenish liquid.
  • Example 15 N-2-aminoethylpiperazine, 1.9 parts (0.015 equivalent) is added to diheptylphenyl phosphorodithioic acid, 379 part (1 equivalent) at 24 C. The mixture is heated to and held at 50-55 C. for 3 hours. The product is a clear, light brown colored liquid.
  • Example 16 To 355 parts (1 equivalent) of diisooctyl phosphorodithioic acid, 17.75 parts (0.125 equivalent) of the amine mixture defined in Example 1 is added with stirring at 55 C. and the mixture is held at 50-55 C. for 3 hours. The product is a clear, light green liquid.
  • Example 17 To 355 parts (1 equivalent) of diisooctyl phosphorodithioic acid is added with stirring 17.75 parts (0.2 equivalent) of .amylamine at 24 C. The mixture is heated to 50 C. and held at 50-55" C. for 3 hours. The product is a clear, light green liquid.
  • Example A An improved zinc phosphorodithioate diester of this invention is prepared by adding 366 parts (1 equivalent) of the improved phosphorodithioic acid diester of Example 1 in one hour, Without heating, to 44.7 parts (1.1 equivalents) of zinc oxide in 65 parts of a parafiin oil having a viscosity of 100 SUS at 100 F., with an exothermic temperature rise to 35 C., heating to 50 C. in one-half hour and holding at 50 C. for one hour.
  • the reaction mixture is heated to C. in 2 hours under vacuum with a pressure drop of from 160 to 125 millimeters and then at 125 millimeters to 120 millimeters while heating to C. in an additional 1.25 hours.
  • the product is filtered with the use of a diatomaceous earth filter aid to yield a clear, bright, light yellow liquid having the follow- ;ing analysis: 6.75% phosphorus, 13.70% sulfur, 7.54%
  • Example B An improved zinc phosphorodithioate diester is prepared by adding 1192 parts (4.0 equivalents) of the phosphorodithioic acid diester of Example 3 in 3.34 hours, Without heating, to 178 parts (4.4 equivalents) of zinc oxide suspended in 204 grams of the oil used in Example A. The temperature rose exothermically from 25 to 50 C. The reaction mixture is held at 50 C. for one hour, heated from 50 to 73 C. in one hour under vacuum with the pressure dropping from 160 to 125 millimeters, and then at 125 to millimeters while heating to 100 C. in an additional 1.5 hours. The product is filtered with the use of a diatomaceous earth filter aid to yield a clear, bright, amber liquid having the following analyses: 9.14% phosphorus, 19.25% sulfur, 9.38% zinc and 0.32% nitrogen.
  • Example D The procedure of Example A is repeated using 252 parts (1 equivalent) of the phosphorodithioic acid diester of Example 4, 44.7 parts (1.1 equivalents) of zinc oxde and 65 parts of oil to obtain an improved zinc phosphorodithioate diester.
  • Example E The procedure of Example A is repeated using the phosphorodithioic acid diester of Example 6, 299 parts (1 equivalent), zinc oxide 44.7 parts (1.1 equivalents) and 65 parts of oil to obtain an improved zinc phosphorodithioate diester.
  • Example F The procedure of Example A is repeated using 378 parts (1 equivalent) of the phosphorodithioic acid prepared in Example 7, 44.7 parts (1.1 equivalents) of z'nc oxide and 65 parts of oil to obtain an improved zinc phosphorodithioate diester.
  • Example G A phosphorodithioic acid ester is prepared according to the procedure of Example 1 using 577 parts (4 equivalents) of nonyl alcohol, 58 parts (0.41 equivalent) of the amine used in Example 1 and 244 parts (1.1 moles) of phosphorus pentasulfide. The procedure of Example A is repeated using 383 parts (1 equivalent) of this phosphorodithioic acid, 44.7 parts (1.1 equivalents) of zinc oxide and 65 parts of oil to obtain an improved zinc phosphorodit'nioate diester of this invention.
  • Example H The procedure of Example A is repeated using 355 parts (1 equivalent) of the phosphorodithioic acid diester of Example 5, 84.4 parts (1.1 equivalents) of barium oxide and 65 parts of oil to obtain an improved barium phosphorodithioate diester of this invention.
  • Example I The procedure of Example A is repeated using 383 parts (1 equivalent) of the phosphorodithioic acid diester of Example 9, 84.4 parts (1.1 equivalents) of barium oxide and 65 parts of oil to obtain an improved barium phosphorodithioate diester.
  • Example J The procedure of Example A is repeated using 253 parts (1 equivalent) of the phosphorodithioic acid diester of Example 8, 84.4 parts (1.1 equivalents) of barium oxide and 65 parts of oil to obtain an improved barium phosphorodithioate diester.
  • the corrosiveness of the phosphorodithioic acid diesters of this invention is shown to be reduced when compared with conventionally prepared diesters by the following test in which the attack upon mild steel is determined in a static corrosion test.
  • the test involves immersing a sample of mild steel of known area in the solution to be tested for a given period of time at a given temperature. The weight loss of the sample is determined and the corrosion rate in inches per year is then calculated. Table I shows the results of such a test:
  • the Group H metal salts of the improved 0,0-phosphorodithioic acid diesters prepared by the novel process herein previously described have utility as inhibitors against oxidation and corrosion in lubricating oils for internal combustion engines.
  • the improved materials made by the process of this invention can be used for a variety of purposes such as, for example, in gear oils, torque-converter oils, turbine oils, turbo-jet oils, cutting oils, greases, hydraulic oils, flotation agents, plasticizers, etc.
  • a lubricating composition comprising a major proportion of a mineral lubricating oil and from about 0.01% to about 2.0% by weight of a Group 11 metal salts of an 0,0-diester of phosphorodithioic acid prepared by (A) forming an improved 0,0'-diester of phosphorodithioic acid by reacting at from about 20 C. to about 200 C.
  • (A) (2)(a) is a primary aliphatic alcohol or a mixture of primary aliphatic alcohols having from 1 to about 30 carbon atoms.
  • (A)(2)(b) is a mixture of heterocyclic amines consisting essentially of 4-(2-aminoethoxy) ethyl morpholine, 2-(4-morpholinylethoxy) ethanol, and bis-2-(4-morpholinyl)ethyl ether said mixture having a nitrogen content of about 11%.

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Description

United States Patent Ofi ice 3,361,668 Patented Jan. 2, 1968 No Drawing. Filed Oct. 19, 1965, Ser. No. 498,107 6 Claims. c1. 2s2 -32.7
This invention relates to a process for preparing light colored and relatively non-corrosive, oil-soluble 0,0- phosphorodithioic acid diesters and metal salts prepared from such 0,0'-phosphorodithioic acid diesters, particularly the zinc salts.
The zinc salts of 0,0-phosphorodithioic acid diesters have long been known to have useful properties as inhibitors of corrosion and oxidation. The are especially useful as additives for crankcase lubricants in internal combustion engines in which service they provide a means of combatting deterioration of the oil and prevent corrosion of the relatively moving surfaces, particularly the bearing surfaces. Their use for such purposes is well established and their usefulness in this capacity has increased with the development and refinement of the modern internal combustion engine.
In normal practice, 0,0'-phosphorodithioic acid diesters are manufactured by reacting about 4 equivalents of an organic monohydroxy compound, e.g., an alcohol or a phenol with one mole of phosphorus pentasulfide at temperatures of from about 50 C. to about 150 C. with the evolution of hydrogen sulfide as illustrated by the following equation:
The oil-soluble metal phosphorodithioate diester salts are usually manufactured by neutralizing the phosphorodithioic acid diester with a basically reacting metal compound, preferably the oxide, frequently With a small amount of water added, at temperatures of from about 50 to about 150 C.
A phosphorodithioic acid diester is usually assumed to have the structure shown in the above equation wherein the thiol group attached to the phosphorus atom accounts for its relatively strong acidic character. In addition, unless the alcohols used are anhydrous, traces of water which are present in the reaction mixture react with the phosphorus pentasulfide causing the formation of small amounts of monesters of phosphorodithioic acid or phosphoromonothioic acid and even some unesterified phosphorus and sulfur containing acids, which may also contribute to their strongly acidic character. In any event, the commercially prepared phosphorodithioic acid diesters are sufiiciently strong acids to be corrosive to metals and the use of special corrosion resistant equipment is generally required in their manufacture and storage. Therefore, the phosphorodithioic acid diesters usually are manufactured in stainless steel or glass lined steel equipment and it is standard practice to store them in stainless steel storage bins.
The trend in recent years in lubricating oil manufacture has been toward producing lighter colored lubricants. This is because of a tendency among both manufacturers and the consuming public to associate the light color of a product with better performance. This is predicated on the fact that the products of lubricant deterioration and the precursors of sludge and varnish in a lubricating oil are usually dark in color. It follows that with the advent of lighter colored lubricating oil compositions, it is imperative that the additives which are incorporated into the oil should also be light in color so as not darken or impart an off color to the lubricant composition.
An object of this invention, therefore, is to provide a process for preparing 0,0'-diesters of phosphorodithioic acid which are less corrosive to metals.
Another object of this invention is to provide a process for preparing light colored 0,0-diesters of phosphorodithioic acid.
It is also an object of this invention to provide a process for preparing 0,0'-diesters of phosphorodithioic acid which can be manufactured and handled in conventional process equipment.
Another object is to provide a process for preparing light colored metal salts of 0,0'-diesters of phosphorodithioic acids.
Still another object of this invention is to provide a process for preparing light colored zinc salts of 0,0-di esters of phosphorodithioic acid.
It is still further an object to provide a process for preparing very light colored compositions which are suitable for use in lubricants intended for use at high temperatures.
These and other objects which will become apparent from the following disclosure are accomplished by a process for preparing improved 0,0'-diesters of phosophorodithioic acid comprising reacting at from about 20 C. to about 200 C., one mole of phosphorus pentasulfide with about 4 equivalents of a mixture of from about to about 99.95% by weight of a monohydroxy organic compound selected from the class consisting of alcohols and phenols and from about 0.05% to about 5% by Weight of an amine selected from the class consisting of alkyl amines, cycloalkyl amines and heterocyclic amines. These objects are also accomplished by a process for preparing improved 0,0-diesters of phosophorodithioic acid comprising reacting from about 95% to about 99.95% by weight of an 0,0-diester of phosphorodithioic acid with from about 0.05% to about 5% by Weight of an amine selected from the class consisting of alkyl amines, cycloalkyl amines and heterocyclic amines.
Light coiored phosphorodithioic acid diesters are obtained by the process of this invention in one of two ways. Either a small amount of a suitable amine is added to the alcohol before the alcohol is reacted with phosphorus pentasulfide or the phosphorodithioic acid diester is first prepared and a small amount of a suitable amine is then added. In either case, the product obtained is appreciably lighter in color than that made by prior art processes without the use of an amine.
t is preferred to mix the amine with the alcohol before reaction with phosphorus pentasulfide in order to take advantage of the reduced corrosiveness of the acid toward the processing equipment during the acid formation.
When the improved phosphorodithioic acid diesters are prepared by reacting a mixture of an alcohol or phenol and an amine with phosphorus pentasulfide, the mixture may contain from about 95 to 99.95% (by weight) of alcohol or phenol and from about 0.05% to 5% of the amine. The ratio of alcohol-amine mixture to phosphorus pentasulfide is about 4 equivalents per mole but an excess of the alcohol or phenol may be used as a solvent for the reaction or an excess of phosphorus pentasulfide may be used if it is desirable to completely consume the alcohol. In the latter case, the excess phosphorus pentasulfide is removed by suitable means such as littering or centrifuging. Preferably, four equivalents of alcohol-amine mixture is reacted with about one mole or slightly more than one mole of phosphorus pentasulfide.
The number of equivalents of the alcohol-amine mixture is their combined number of equivalents. Since the alcohols or phenols preferred in the process are monohydric alcohols, the equivalent Weight of such alcohol or phenol is its molecular weight. The equivalent weight of the amine is its molecular weight divided by the number of nitrogen atoms in the molecule. Thus, a monoamine has one equivalent per mole, a diamine has two equivalents per mole, a triamine has three equivalents per mole, etc.
The acid forming reaction is usually carried out by the slow, continuous addition of phosphorus pentasulfide or by the addition of small, discrete increments of phosphorus pentasulfide to the alcohol-amine mixture. The acid can also 'be manufactured in a continuous process such as that described in US. Patent No. 2,862,947 wherein both alcohol and P 3 are added continuously to a reaction zone and the acid product is continuously removed. Reaction may be effected :at temperatures of from about 20 to about 200 C. The preferred temperature range is from about 60 C. to about 130 C.
When the previously manufactured phosphorodithioic acid diester is treated with an amine, about 0.05% to 5% by weight of the amine is reacted with the phosphorodithioic acid dies-ter at temperatures of from about 20 to about 200 C.
Suitable monohydroxy organic compounds useful in the preparation of the improved 0,0'-diesters of phosphorodithioic acid include alcohols, phenols, and alkyl phenols, including their substituted derivatives, e.g., nitro-, halo-, alkoxy-, hydroxy-, carboxy-, etc. Suitable alcohols include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, Z-butanol, Z-methyl-propanol, n-pentanol, 2- pentanol, 3-pentanol, 2-methylbutanol, 3-methyl-2-pentanol, n-hexanol, 2-hexanol, 3-hexanol, Z-methyl-Z-pentanol, 4-methyl-3-pentanol, cyclohexanol, chlorocyclohexanol, methylcyclohexanol, heptanol, 2-ethylhexanol, n-octanol, 2,2-dimethyloctanol, nonanol, dodecanol, octadecanol, eicosanol, etc. The phenols suitable for the purposes of this invention include alkyl phenols and substituted phenols, e.g., phenol, chlorophenol, bromophenol, nitrophenol, methoxyphenol, cresol, propylphenol, butylphenol, amylphenol, heptylphenol, octylphenol, nonylphenol, octadecylphenol, etc. Ordinarily, the monohydroxy organic compounds su-itable for purposes of this invention may have from 1 to about 30 carbon atoms.
In the interest of obtaining phosphorodithioic acid diesters whose metal salts have high phosphor-usand sulfur-content as well as being oil-soluble, a mixture of high molecular weight and low molecular weight alcohols may be used. The use of mixtures of alcohols also enables the utilization of cheaper alcohols which by themselves do not yield oil-soluble phosphorodithioate acid salts. Thus, a mixture of isopropyl and hexyl alcohols can be used to produce a very effective oil-soluble metal phosphorodithioate. For the same reason, mixtures of simple acids, i.e., acids prepared from single alcohol can be reacted with the metal neutralizing agent to produce less expensive, oil-soluble metal salts.
The amines suitable for use in this invention for preparing the improved phosphorodithioic acid diester and their metal salts include the primary, secondary, and tertiary alkylamines and cycloalkylamines. Examples of such suitable amines include ethylamine, propylamine, isopropylarnine, butylarnine, isobutylamine, tertiary butylamine, n-pentylamine, isopentylamine, 3-methyl-2 butylamine, nhexylamine, Z-methylpentylamine, Z-ethylbutylamine, 2,2- dimethylbutylamine, n-heptylamine, Z-methylhexylamine, 3-methylhexylamine, 2-ethylpentylamine, n-octylamine, 2-ethylhexylamine, 2,2-dimethyldodecylamine, dimethylamine, diethylamine, dipropylarnine, diisopropylarnine, dibutylamine, diisobutylamine, dipentylamine, di-2-rnethylpentylamine, diheptylamine, di-Z-ethylhexylamine, diisooctylamine, didecylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, benzylamine, furfurylamine, cyclohexylamine, dicyclohexylamine, etc.
Also useful for the purposes of this invention are the heterocyclic amines, that is, amines in which the amino nitrogenatom is a part of a ring made up of dissimilar atoms such as carbon, oxygen and sulfur as well as nitrogen. Examples of such heterocyclic amines include pyrrole, dihydropyrrole, pyrrolidine, oxazolidine, isoxazolidine, thiazolidine, oxazidine, piperidine, piperazine, morpholine, 4-(Z-aminoethoxy)ethylmorpholine, 2-(4-morpholinylethoxy)ethanol, bis-2- (4-morpholinyl)ethyl ether,
etc. i
The improved metal salts of 0,0-diesters of phosphorodithioic acid of this invention are preferably salts of metals in Group II of the Periodic Table and comprise the salts of calcium, barium, strontium, zinc, and cadmium. The zinc and barium phosphorodithioate diesters are particularly effective as additives in lubricating compositions and are therefore preferred for use herein.
The preparation of metal salts of the phosphorodithioic acid diesters is well-nown. They are prepared, for example, by the reaction of the acid with a metal neutralizing agent such as zinc, zinc oxide, or barium oxide. Simply mixing and heating these reactants is suflicient to cause the neutralization to take place and the resulting product is sufiiciently pure for the purpose of this invention.
The following examples are illustrative of the process of preparing the improved phosphorodithioic acid diesters of this invention:
Example 1 A mixture of 381 parts (2.93 equivalents) of isooctanol and 4 parts (0.028 equivalent) of a heterocyclic amine mixture consisting essentially of 4-(2-aminoethoxy) ethylmorpholine, 2-(4-morpholinylethoxy)ethanol, and bis-2-(4-morpholinyl)ethy1 ether and having a nitrogen content of about 11% and an equivalent weight of about 142 is heated to 75 C. in one hour and 164 parts (0.74 mole) of phosphorus pentasulfide is added in one hour at 75-90 C. The reaction mixture is held at 100 C. for one hour and is filtered through a diatomaceous earth filter pad to obtain a clear, very light green liquid which is found to contain 17.37% sulfur, 8.05% phosphorus, 0.02% nitrogen.
Example 2 A mixture of 1213 parts (16.4 equivalents) of isobutanol, 779 parts (8.83 equivalents) of primary amyl alcohol, and parts (0.67 equivalent) of the amine used in Example 1 is heated to 70 C. and 1368 parts (6.17 moles) of phosphorus pentasulfide is added at 7075 C. in 3 hours. The reaction mixture is heated for 1% hours at 7585 C. and filtered. The filtrate (3158 parts). is a clear, light green liquid containing 11.7% phosphorus, 24.8% sulfur, and 0.35% nitrogen.
Example 4 A mixture of 96 parts (1.3 equivalents) of isobutanol, 61.6 parts (0.70 equivalent) of a primary amyl alcohol, 1.6 parts (0.011 equivalent) of the amine used in Example l is heated to 70 C. and 111 parts (0.5 mole) of phosphorus pentasulfide is added at 70-75 C. in one hour. The reaction mixture is heated anadditional hour at 7S-85 C. and then filtered. The filtrate is the product;
Example 5 The process of Example 1 is repeated except that the quantity of iso-octa-nol used is 398 parts (3.06 equivalents), the quantity of amine used is 2 grams (0.014 equivalent), and the quantity of phosphorus pentasulfide is 171 parts (0.77 mole).
Example V A mixture of 204 parts (2 equivalents) of 3-methyl-2- pentanol and2 parts (0.23 equivalent) of amylarnine is heated to 80 C. and 111 parts (0.5 mole) of phosphorus pentasulfide is added at 8085 C. in one hour. The reaction mixture is heated for one hour at 90-95 C. and filtered. The filtrate is the product.
Example 7 To a mixture of 500 parts (2.6 equivalents) of heptylphenol and 25 parts (0.135 equivalent) of dodecylamine is added 155 parts (0.7 mole) of phosphorus pentasulfide at 75-85 C. in one hour. The reaction mixture is heated one hour at 100-105 C. and filtered. The filtrate is the product.
Example 8 A mixture of 245 parts (2.4 equivalents) of 3-methyl- 2-pentanol, 96 parts (1.6 equivalents) of isopropanol, and 3.4 parts (0.034 equivalent) of cyclohexylamine is heated to 70 C. and 222 parts (1.0 mole) of phosphorus pentasulfide is added in one hour. The mixture is held at 80- 90 C. for one hour and filtered. The filtrate is the product.
Example 9 Phosphorus pentasulfide, 112 parts (0.5 mole) is added to a mixture of 288 parts (2 equivalents) of nonyl alcohol and 2.9 parts (0.029 equivalent) of dipropylamine at 75- 85 C. in one hour and the reaction mixture is heated for one hour at 7585 C. before filtration.
Example 10 To 355 parts (1 equivalent) of diisooctyl phosphorodithioic acid, 3.6 parts (0.025 equivalent) of the amine mixture defined in Example 1 is added with stirring at 55 C. and held at 5055 C. for 3 hours. The product is a clear, light green liquid.
Example 11 Amylamine, 3.6 parts (0.04 equivalent) is added to diisooctyl phosphorodithioic acid, 355 parts (1 equivalent) at 24 C. The mixture is heated to 50 C. and held at that temperature for 3 hours. The product is a clear, light green liquid.
Example 12 The amine mixture defined in Example 1, 2.5 parts (0.018 equivalent) is added at ambient temperature to 252 parts (1 equivalent) of a dialkylphosphorodithioic acid made from a 65 mole percent isobutyl alcohol-35 mole percent primary amyl alcohol mixture. The mixture is heated to 50 C. and held at this temperature for 3 hours. The product is a clear, greenish liquid.
Example 13 Amylamine, 2.5 parts (0.029 equivalent) is added to 252 parts (1 equivalent) of the dialkylphosphorodithioic acid used in Example 12 at 24 C. The mixture is heated to 50 C. and held at that temperature for 3 hours. The product is a greenish, clear liquid.
Example 14 To 298 parts 1.0 equivalent) of di-4-methyl-2-pentyl phosphorodithioic acid, 3 parts (0.03 equivalent) of dipropylamine is added at 24 C. The mixture is heated to 50 C. and held at that temperature for 3 hours. The product is a clear, greenish liquid.
Example 15 N-2-aminoethylpiperazine, 1.9 parts (0.015 equivalent) is added to diheptylphenyl phosphorodithioic acid, 379 part (1 equivalent) at 24 C. The mixture is heated to and held at 50-55 C. for 3 hours. The product is a clear, light brown colored liquid.
Example 16 To 355 parts (1 equivalent) of diisooctyl phosphorodithioic acid, 17.75 parts (0.125 equivalent) of the amine mixture defined in Example 1 is added with stirring at 55 C. and the mixture is held at 50-55 C. for 3 hours. The product is a clear, light green liquid.
Example 17 To 355 parts (1 equivalent) of diisooctyl phosphorodithioic acid is added with stirring 17.75 parts (0.2 equivalent) of .amylamine at 24 C. The mixture is heated to 50 C. and held at 50-55" C. for 3 hours. The product is a clear, light green liquid.
The following examples show preferred methods of preparing the improved Group II metal salts of 0,0- phosphorodithioic acid diesters:
Example A An improved zinc phosphorodithioate diester of this invention is prepared by adding 366 parts (1 equivalent) of the improved phosphorodithioic acid diester of Example 1 in one hour, Without heating, to 44.7 parts (1.1 equivalents) of zinc oxide in 65 parts of a parafiin oil having a viscosity of 100 SUS at 100 F., with an exothermic temperature rise to 35 C., heating to 50 C. in one-half hour and holding at 50 C. for one hour. The reaction mixture is heated to C. in 2 hours under vacuum with a pressure drop of from 160 to 125 millimeters and then at 125 millimeters to 120 millimeters while heating to C. in an additional 1.25 hours. The product is filtered with the use of a diatomaceous earth filter aid to yield a clear, bright, light yellow liquid having the follow- ;ing analysis: 6.75% phosphorus, 13.70% sulfur, 7.54%
zinc and 0.01% nitrogen.
Example B Example C An improved zinc phosphorodithioate diester is prepared by adding 1192 parts (4.0 equivalents) of the phosphorodithioic acid diester of Example 3 in 3.34 hours, Without heating, to 178 parts (4.4 equivalents) of zinc oxide suspended in 204 grams of the oil used in Example A. The temperature rose exothermically from 25 to 50 C. The reaction mixture is held at 50 C. for one hour, heated from 50 to 73 C. in one hour under vacuum with the pressure dropping from 160 to 125 millimeters, and then at 125 to millimeters while heating to 100 C. in an additional 1.5 hours. The product is filtered with the use of a diatomaceous earth filter aid to yield a clear, bright, amber liquid having the following analyses: 9.14% phosphorus, 19.25% sulfur, 9.38% zinc and 0.32% nitrogen.
Example D The procedure of Example A is repeated using 252 parts (1 equivalent) of the phosphorodithioic acid diester of Example 4, 44.7 parts (1.1 equivalents) of zinc oxde and 65 parts of oil to obtain an improved zinc phosphorodithioate diester.
Example E The procedure of Example A is repeated using the phosphorodithioic acid diester of Example 6, 299 parts (1 equivalent), zinc oxide 44.7 parts (1.1 equivalents) and 65 parts of oil to obtain an improved zinc phosphorodithioate diester.
Example F The procedure of Example A is repeated using 378 parts (1 equivalent) of the phosphorodithioic acid prepared in Example 7, 44.7 parts (1.1 equivalents) of z'nc oxide and 65 parts of oil to obtain an improved zinc phosphorodithioate diester.
Example G A phosphorodithioic acid ester is prepared according to the procedure of Example 1 using 577 parts (4 equivalents) of nonyl alcohol, 58 parts (0.41 equivalent) of the amine used in Example 1 and 244 parts (1.1 moles) of phosphorus pentasulfide. The procedure of Example A is repeated using 383 parts (1 equivalent) of this phosphorodithioic acid, 44.7 parts (1.1 equivalents) of zinc oxide and 65 parts of oil to obtain an improved zinc phosphorodit'nioate diester of this invention.
Example H The procedure of Example A is repeated using 355 parts (1 equivalent) of the phosphorodithioic acid diester of Example 5, 84.4 parts (1.1 equivalents) of barium oxide and 65 parts of oil to obtain an improved barium phosphorodithioate diester of this invention.
Example I The procedure of Example A is repeated using 383 parts (1 equivalent) of the phosphorodithioic acid diester of Example 9, 84.4 parts (1.1 equivalents) of barium oxide and 65 parts of oil to obtain an improved barium phosphorodithioate diester.
Example J The procedure of Example A is repeated using 253 parts (1 equivalent) of the phosphorodithioic acid diester of Example 8, 84.4 parts (1.1 equivalents) of barium oxide and 65 parts of oil to obtain an improved barium phosphorodithioate diester.
The corrosiveness of the phosphorodithioic acid diesters of this invention is shown to be reduced when compared with conventionally prepared diesters by the following test in which the attack upon mild steel is determined in a static corrosion test. The test involves immersing a sample of mild steel of known area in the solution to be tested for a given period of time at a given temperature. The weight loss of the sample is determined and the corrosion rate in inches per year is then calculated. Table I shows the results of such a test:
TABLE I Corrosion Solution Tested Temperature Rate (inches per year) The product of Example 2 Room temperature 0. 0017 100% diisooctylphosphorodo H 0. 0884 dithioic acid.
TABLE II Solution Tested: Color Eroduct of Example 5.5 Product of Example 11 5.5 Product of Example 16 5.5 Product of Example 17 4.5
Diisooctylphosphorodithioic acid 7.0
The Group H metal salts of the improved 0,0-phosphorodithioic acid diesters prepared by the novel process herein previously described have utility as inhibitors against oxidation and corrosion in lubricating oils for internal combustion engines. However, it should be understood that the improved materials made by the process of this invention can be used for a variety of purposes such as, for example, in gear oils, torque-converter oils, turbine oils, turbo-jet oils, cutting oils, greases, hydraulic oils, flotation agents, plasticizers, etc.
Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated inany of the following claims, or the equivalent of such, be employed.
I claim:
1. A lubricating composition comprising a major proportion of a mineral lubricating oil and from about 0.01% to about 2.0% by weight of a Group 11 metal salts of an 0,0-diester of phosphorodithioic acid prepared by (A) forming an improved 0,0'-diester of phosphorodithioic acid by reacting at from about 20 C. to about 200 C.
(1) 1 mole of phosphorus pentasulfide with (2) about 4 equivalents of a mixture of (a) from about to about 99.95% by weight of a monohydroxy alcohol or phenol having from 1 to about 30 ctrbon atoms and (b) from about 0.05% to about 5% by weight of an alkyl amine, cycloalkylamine or heterocyclic amine having up to about 20 carbon atoms and (B) reacting said 0,0'-diester of phosphorodithioic acid with about an equivalent amount oi a basic reacting Group 11 metal compound.
2. The lubrication composition of claim 1 wherein (A) (2)(a) is a primary aliphatic alcohol or a mixture of primary aliphatic alcohols having from 1 to about 30 carbon atoms.
3. The lubricating composition of claim 1 wherein (A) (2)(a) is phenol or an alkylphenol having up to about 30 carbon atoms.
4. The lubricating composition of claim 1 wherein (A) (2)(b) is a heterocyclic amine having up to about 12 carbon atoms.
5. The lubricating composition of claim 1 wherein (A)(2)(b) is a mixture of heterocyclic amines consisting essentially of 4-(2-aminoethoxy) ethyl morpholine, 2-(4-morpholinylethoxy) ethanol, and bis-2-(4-morpholinyl)ethyl ether said mixture having a nitrogen content of about 11%.
6. The lubricating composition of claim 1 wherein the basic reacting Group 11 metal compound is a zinc compound.
References Cited UNITED STATES PATENTS 2,983,742 5/1961 Boba et a1. 26098l 3,000,822 9/l96l Higgins et a1. 25232.7 3,029,268 4/ 1962 Goldsmith 25232.7 3,267,033 8/1966 Allen 25232.7 3,281,356 10/1966 Coleman 25232.7 3,284,548 ll/1966 \Vicrber 25232.7
DANIEL E. WYMAN, Primary Examiner.
W. H. CANNON, L. G. XIARHOS, Assistant Examiners.

Claims (1)

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTION OF A MINERAL LUBRICATING OIL AND FROM ABUT 0.01% TO ABOUT 2.0% BY WEIGHT FO A GROUP II METAL SALTS OF AN O,O''-DIESTER OF PHOSPHORODITHIOIC ACID PREPARED BY (A) FORMING AN IMPROVED O,O''-DIESTER OF PHOSPHORODITHIOIC ACID BY REACTING AT FROM ABOUT 20*C. (1) 1 MOLE OF PHOSPHORUS PENTASULFIDE WITH (2) ABOUT 4 EQUIVALENTS OF A MIXTURE OF (A) FROM ABOUT 95% TO ABOUT 99.95% BY WEIGHT OF A MONOHYDROXY ALCOHOL OR PHENOL (B) FROM ABOUT 3.35% TO ABOUT 5% BY HAVING FROM 1 TO ABOUT 30 CARBON ATOMS AND (B) FROM ABOUT 0.05% TO ABOUT 5% BY WEIGHT OF AN ALKYL AMINE, CYCLOALKYLAMINE OR HETEROCYCLIC AMINE HAVING UP TO ABOUT 20 CARBON ATOMS AND (B) REACTING SAID O,O''-DIESTER OF PHOSPHORODITHIOIC ACID WITH ABOUT AN EQUIVALENT AMOUNT OF A BASIC REACTING GROUP II METAL COMPOUND.
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US3471540A (en) * 1967-03-22 1969-10-07 Phillips Petroleum Co Production of metal salts of dihydrocarbyldithiophosphoric acids
US3619167A (en) * 1967-09-27 1971-11-09 Ici Ltd Herbicidal compositions containing bipyridylium salts with reduced corrosiveness toward metals
US4049755A (en) * 1974-01-11 1977-09-20 Montedison S.P.A. Process for preparing O,O-dimethyldithiophosphoric acid and alkaline salts thereof
US4215067A (en) * 1978-12-29 1980-07-29 Standard Oil Company (Indiana) Process for the preparation of zinc salts of dihydrocarbyldithiophosphoric acids
US4496495A (en) * 1983-01-12 1985-01-29 Standard Oil Company (Indiana) Stabilization of phosphorodithioic acid diesters
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US3471540A (en) * 1967-03-22 1969-10-07 Phillips Petroleum Co Production of metal salts of dihydrocarbyldithiophosphoric acids
US3619167A (en) * 1967-09-27 1971-11-09 Ici Ltd Herbicidal compositions containing bipyridylium salts with reduced corrosiveness toward metals
US4049755A (en) * 1974-01-11 1977-09-20 Montedison S.P.A. Process for preparing O,O-dimethyldithiophosphoric acid and alkaline salts thereof
US4215067A (en) * 1978-12-29 1980-07-29 Standard Oil Company (Indiana) Process for the preparation of zinc salts of dihydrocarbyldithiophosphoric acids
US4496495A (en) * 1983-01-12 1985-01-29 Standard Oil Company (Indiana) Stabilization of phosphorodithioic acid diesters
US4618450A (en) * 1984-11-07 1986-10-21 The Lubrizol Corporation Aqueous systems containing amino sulfonic acid derivatives of carboxylic acids
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WO1986006378A1 (en) * 1985-04-29 1986-11-06 The Lubrizol Corporation Metal salts of mixed aromatic/aliphatic phosphorodithioic acids
FR2602234A1 (en) * 1986-08-01 1988-02-05 Shell Int Research PROCESS FOR THIOPHOSPHORYLATION OF ALCOHOLS AND USE OF THE PRODUCT OBTAINED AS AN INTERMEDIATE IN THE PREPARATION OF ADDITIVES FOR LUBRICATING OILS
US5308517A (en) * 1993-02-22 1994-05-03 Exxon Research & Engineering Co. Ashless lube additives containing complexes of alkoxylated amines, dihydrocarbyldithiophosphoric acid, and adenine
CN105247007A (en) * 2013-03-15 2016-01-13 克利尔沃尔特国际有限责任公司 Environmentally friendly quaternary salts of amines and their use as temporary and/or permanent clay stabilizers and methods for making and using same
EP2970746A4 (en) * 2013-03-15 2016-11-02 Lubrizol Oilfield Solutions Inc Environmentally friendly quaternary salts of amines and their use as temporary and/or permanent clay stabilizers and methods for making and using same
EP2970005A4 (en) * 2013-03-15 2016-12-21 Lubrizol Oilfield Solutions Inc Environmentally friendly permanent quaternaries of polyamines and their use as clay stabilizers and methods for making and using same
EP2930229A1 (en) * 2014-04-09 2015-10-14 Afton Chemical Corporation Boron-free corrosion inhibitors for metalworking fluids
US9828566B2 (en) 2015-07-06 2017-11-28 Afton Checmical Corporation Boron free corrosion inhibitors for metalworking fluids

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