US2535024A - Lubricating compositions - Google Patents
Lubricating compositions Download PDFInfo
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- US2535024A US2535024A US2132A US213248A US2535024A US 2535024 A US2535024 A US 2535024A US 2132 A US2132 A US 2132A US 213248 A US213248 A US 213248A US 2535024 A US2535024 A US 2535024A
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- methanol
- oil
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- dithiophosphoric acid
- dithiophosphoric
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- 239000000203 mixture Substances 0.000 title description 10
- 230000001050 lubricating effect Effects 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 103
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 22
- 238000006386 neutralization reaction Methods 0.000 claims description 20
- 239000002480 mineral oil Substances 0.000 claims description 17
- 235000010446 mineral oil Nutrition 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 229910001385 heavy metal Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 32
- 150000002148 esters Chemical class 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- -1 dithiophosphoric acid ester Chemical class 0.000 description 10
- 239000010687 lubricating oil Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- TXPYHRFTMYVSLD-UHFFFAOYSA-N 2,3,4-tris(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=C(O)C(CC(C)C)=C1CC(C)C TXPYHRFTMYVSLD-UHFFFAOYSA-N 0.000 description 1
- IXKVYSRDIVLASR-UHFFFAOYSA-N 2,3-dioctylphenol Chemical compound CCCCCCCCC1=CC=CC(O)=C1CCCCCCCC IXKVYSRDIVLASR-UHFFFAOYSA-N 0.000 description 1
- BAYAKMPRFGNNFW-UHFFFAOYSA-N 2,4-dimethylpentan-3-ol Chemical compound CC(C)C(O)C(C)C BAYAKMPRFGNNFW-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 229960005382 phenolphthalein Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
Definitions
- these dithiophosphoric acid esters may advantageously be carried out in a mineral oil solution and/or dispersion in the presence 01' an amount of methanol small enough as to render its subsequent removal unnecessary.
- Example 2 A mixture of alcohols and phenols composed of 20% octyl phenol, 20% methyl isobutyl carbinol, 10% capryl alcohol, and the balance a distillation fraction of the by-product alcohols obtained in the synthesis of methanol, boiling between 160 C. and 200 C. and consisting predominantly of 7 and 8 carbon atom alcohols, and described in U. S. Patent No. 2,368,000 was treated with P285 to form the corresponding mixed diester of dithiophosphoric acid. The equivalent weight of this acid product was 450.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Description
Patented Dec. 26, 1950 2,535,024 LUBRIOATING COMPOSITIONS Charles Earle Funk, Jr., Cos Cob, Conn., assignm- -to American Cyanamid Company, New York, N. Y., a corporation of Maine e No Drawing. Application January 13, 1948.
Serial No. 2,132
3 Claims.
This invention relates to the production of improvement agents for lubricating oils, and relates more particularly to the production of mineral oil solutions of heavy metal salts of esters of dithiophosphoric acid which are suitable for use as antioxidant and detergent agents in the improvement of lubricating oils. The present application is a continuation-in-part of application Serial No. 643,749, filed January 26, 1948 (now abandoned).
Lubricating oil addition agents having particularly desirable detergent and antioxidant qualities are the heavy metal salts of esters of dithiophosphoric acid, which are formed by reacting alkyl or alkaryl compounds with phosphorus pentasulflde and neutralizing the acids so produced with oxides or hydroxides containing various heavy metals such as calcium, barium, zinc, tin, and the like.
Heretofore. it has been necessary to carry out the dithiophosphoric acid ester neutralization in the presence of polar and non-polar solvents such as solvent mixtures comprising small amounts of the lower alcohols together with greater amounts of indifferent volatile hydrocarbon solvents such as toluol, and the like. 'I'he non-polar solvents acted as diluents for the reactants, while the polar solvents furnished the ionizable medium necessary for the reaction between the esters of dithiophosphoric acid and the basic materials employed. In some instances, it has also been practicable to employ water instead of the above men- 2 these dithiophosphoric acid esters may advantageously be carried out in a mineral oil solution and/or dispersion in the presence 01' an amount of methanol small enough as to render its subsequent removal unnecessary.
Thus the primary object of this invention resides in the provision of a method of producing heavy metal salts of esters of dithiophosphoric acid in mineral oil solution and/or dispersion, whereby solvent recovering may be dispensed with, resulting in the elimination of a troublesome and expensive operational procedure.
A further object oi the invention is the prevention of decomposition of these improvement agents for lubricating oils by the elimination of the relatively high temperatures which have previously been necessary for effecting removal of solvent material therefrom.
In its broader aspects the method of my in- 2 vention consists in the addition of an ester of tioned solvents to provide a medium in which the reactants possessed mutual solubility. The use of these solvents was decidedly disadvantageous because it was necessary to strip the solvent materials subsequent to the salt-forming treatment. Solvent removal was necessary because the presence of such materials in the addition agents in amounts in excess of about 5% caused a lowering of the flash point of the oils to which they are added below the specifications which have been adopted by the industry. Ordinarily, the stripping of the solvents from the additives was carried out either at relatively elevated temperatures or under reduced pressure at somewhat lower temperatures. When the solvent removal was carried out at elevated temperatures there was great danger that the lubricating oil additive would undergo excessive deterioration. When the solvent removal was carried out by resorting to reduced pressure at relatively lower temperatures, the cost of the operation was almost prohibitive.
I have discovered that the neutralization of dithiophosphoric acid to'a dispersion in mineral oil of an oxide or hydroxide of a heavy metal in the presence of a small amount oi methanol. The dithiophosphoric acid esters suitable for use in the present invention include monoalkyl, dialkyl, monoalkaryl, and dialkaryl esters of dithiophosphoric acid which may be produced from primary alcohols such as 2-methyl pentanol-l, 2,4-dimethyl pentanol-l, ii-methyl hexanol-l, 4- methyl heptanol-l, and the like, and secondary alcohols such as di-isopropyl carbinol, and the like. Alkaryl compounds which are exceptionally suitable for producing these dithiophosphoric acid esters include monoand di-alkyl phenols, including tri-isobutyl phenol, di-octyl phenol, and the like compounds.
Neutralization of the above described acid materials may be carried out over a relatively wide temperature range, as for example from about 20 C. to about C. Although the neutralization may be carried out at somewhat higher temperatures, dependent on the amount of methanol present, I have found that best results are obtained when operating within the above-stated temperature range.
I have also found that the amount of methanol which may be satisfactorily employed in the method of my invention, so that the neutralization 01' the dithiophosphoric acid esters will proceed to completion without interruption is within the range of from about 0.5% to about 5.0% based on the weight of the salt-oil solution. While the amount of methanol depends, to some extent on the composition of the mixture, ordinarily from about 1% to about 2-3% will permit the neutralization reaction to proceed satisfactorily. This amount of methanol may be added to the oil and substantially all of it remains in the solution without .causing turbidity in the final dithiophosphoric acid ester-in-oil solution. Furthermore, and entirely unexpectedly, I have found that despite the presence of this small amount of methanol, the flash point of the lubricating oil compounded with the so-prepared addition agents is not lowered.
Thus, I have provided a novel method for the neutralization of esters of dithiophosphoric acids which eliminates the necessity for removal of the solvent material, and results in a neutral solution of the salt in mineral oil by the inclusion, in the neutralizing medium, of an amount of methanol not substantially greater than 5 based on the weight of the salt-oil solution. In my Patent No.i2,466,408 I have described a method wherein, in certain instances, a small amount of water is employed instead of the methanol of the present invention.
In carrying out the method of the invention the dithiophosphoric acid ester is added with vigorous agitation to a suspension in mineral oil, containing from 0.5% to 5.0% of methanol, of an oxide or hydroxide such as barium oxide, or the like. The oil suspension containing the neutralizing agent may be preheated, if desired, to from about 50 C. to about 70 C. before addition of the acid ester and the neutralization reaction, being of an exothermic nature, is controlled by cooling to a temperature not exceeding about 90 C. during the addition of the acid ester. Inasmuch as the boiling point of methanol is approximately 65 C., it might be expected that evaporation thereof would occur at those neutralization temperatures given above which are in excess of 65 0., thus leaving the solutions and/or dispersions free of the methanol solvent and causing the reaction to stop. However, it is also a well-recognized scientific fact that the boiling point of any solvent is raised by the addition thereto of a non-volatile solute. Although the .usual physical chemistry textbook equations of Raoults law permit the calculation of the elevation of boiling points when the solutions involved are quite dilute, by employing a variation of these equations it may be estimated with a reasonable degree of certainty that my neutralized dithiophosphoric acid ester salt-oil solution containing not more than 5% methanol will not boil below about 90 (3., and that solutions containing lesser amounts of methanol will have appreciably higher boiling points.
In practicing the present invention, it has been found that methanol is still present after completing the neutralization treatment even though temperatures as high as 90 C. have been employed. It is to be understood, however, that there is some small degree of evaporation of the methanol since the neutralization step is usually carried out in open vessels. However, the amount of methanol remaining in the solution has not been reduced below that amount necessary to carry out complete neutralization of the acid dithiophosphoric esters, which is usually about 0.5%, based on the weight of the salt-oil solution.
I have found that, in carrying out the neutralization treatment, optimum results are obtained when the quantity of acid ester employed is substantially equal to, but not greater than, the quantity of oil in the dispersion containing the base material and methanol. The neutraliz ing agent employed may range from about 1 to tained by the preparation of a neutral solutions of 50% dilution, of the heavy metal salts of esters of dithiophosphoric acid in mineral oil containing up to about 2% of methanol after filtration of the solution to remove excess neutralizing agent and oil-insoluble salts formed during the neutralization reaction.
Ordinarily, the mineral oil solutions of heavy metal salts of dithiophosphoric acid esters obtained by the method of my invention are clear liquids, indicative of the substantial absence of water. During the neutralization reaction one of the by-products formed is water which, if it exists in the final product in appreciable excess of about 0.3% of the total volume of solution, will cause slight turbidity of the acid salt-mineral oil solution. If it is desirable to remove such excess water, for the purpose of improving the appearance of the solution, the neutralized solutions and/or dispersions may be subjected to "flash stripping, wherein the material is momentarily heated after which the heated material is admitted to an evacuated chamber, permitting the almost instantaneous evaporation of most of the water and methanol along with a simultaneous lowering of the temperature of the liquid. Alternatively, it may be desirable to remove any excess of water by the addition of a small amount of CaSO4 such as anhydrite or calcined gypsum to the solution and/or dispersion. After filtration, the mineral oil solution of the heavy metal salt of the dithiophosphoric acid ester will be entirely clear, the small amount of methanol still present causing no turbidity of the solution. There is no actual need for removing the excess water inasmuch as it does not detract from the antioxidant and detergent qualities of the improvement agent.
The invention will be illustrated in greater detail by the following examples showing specific embodiments thereof. The examples, however, are intended for purposes of illustration only, the limits of the invention being defined by the appended claims.
Example 1 In the preparation of an ester of dithiophosphoric acid there was employed a mixture of alcohols obtained by the catalytic hydrogenation of coconut oil, containing straight-chain alcohols of from 3 carbon atoms to 18 carbon atoms content, which is described in Example 4 of U. S. Patent No. 2,005,619. In this example, lbs. of the alcohol mixture and 34 lbs. of P285 were heated for 2 /2 hours to yield lbs. of a mixed dithiophosphoric acid ester. This acid mixture was I added to an S. A. E. 10 grade lubricating oilbarium oxide-methanol slurry which contained 1.13 lbs. of oil and 0.2 lb. of BaO per pound of acid employed. The amount of methanol was approximately 2% of the product. The acid addition was started with the oil, etc., slurry at a temperature of 25 C., the temperature rising to, and being held at, 50 C. during the reaction. After filtering to remove oil-insoluble salts formed during the neutralization reaction and excess BaO, the solution contained about 0.3% of water, which was reduced to 0.2% by the addition of a small amount of @1804 followed by filtration. The product was a clear solution which had a Saybolt viscosity of 112.4 at F.
The addition agent so prepared was added in an amount of 2% by volume to a commercial 5 lubricating oil. Tests of the lubricating oil containing the additive showed that the flash point of the oil had not been lowered by the addition of the agent. This material was tested in a Chevrolet automobile engine in a continuous run of 36 hours. Test results are as follows:
Addition Agent Addition Agent Containing 2% Prepared by Methanol Prepared Prior Method by the Method of Employing Solvent the Present Removal Pro- Invention cedure Total sludge and varnish rating 99. 3 93. Bearing corrosion, weight loss in gms 0. 039 l. 558 Viscosity SUS at 100 F;
New 172 178 The total sludge and varnish rating is based on inspection of the cylinders, pistons, and piston rings for varnish deposition, and on inspection of the oil for sludge content. Total absence of both is given a rating of 100.
Example 2 A mixture of alcohols and phenols composed of 20% octyl phenol, 20% methyl isobutyl carbinol, 10% capryl alcohol, and the balance a distillation fraction of the by-product alcohols obtained in the synthesis of methanol, boiling between 160 C. and 200 C. and consisting predominantly of 7 and 8 carbon atom alcohols, and described in U. S. Patent No. 2,368,000 was treated with P285 to form the corresponding mixed diester of dithiophosphoric acid. The equivalent weight of this acid product was 450.
159 grams of S. A. E. 10 grade lubricating oil, 28 grams of barium oxide, and 16 grams of methanol was charged to a 1 liter flask fitted with a mechanical agitator, and to which a condenser was attached. The weight of the methanol was calculated so as to be about by weight of the finished product. The mixture was heated to 70 C. and 138 grams of the above described diester of dithiophosphoric acid was added over a period of about minutes. The temperature rose to 76 C. as a result of the reaction. The resulting mixture was heated and stirred for minutes at a temperature of 80 C.-90 C. The product gave an alkaline test to phenol-phthalein indicator, showing the neutralization to be complete. The resulting solution or dispersion was filtered, the filtrate being clear and bright and entirely suitable for use as a lubricating oil addition agent without further treatment. An examination of the condenser and receiver at the end of the experiment showed that less than 1 gram of methanol had been lost by evaporation.
From the foregoing description it will be readily apparent that the present invention provides a method of preparin antioxidant and detergent agents whereby the process has been rendered moreeconomically practicable than those of prior use, and the products exhibit increased effectiveness over those previously obtained by other methods, by the provision of a method of preparing dithiophosphoric acid ester salts in mineral oil solution and/or dispersion, and wherein the removal of solvent material i rendered unnecessary.
What I claim is:
1. Process for preparing a solution in mineral oil of a heavy metal salt of an oil-soluble ester of dithiophosphoric acid which comprises the steps of adding an oil-soluble ester of dithiophosphoric acid to a dispersion in mineral oil of a member of the group consisting of the oxide and hydroxide of barium, said dispersion containing from about 0.5% to about 5.0% of methanol, reacting the said materials at a temperature of from about 20 C. to about C. while retaining in the solution an amount of methanol suflicient to carry out complete neutralization of the acid dithiophosphoric ester, and removing the oil-soluble reaction salts by filtration.
2. Process for preparing a solution in mineral oil of a. heavy metal salt of an oil-soluble ester of dithiophosphoric acid which comprises the steps of adding an oil-soluble ester of dithiophosphoric acid to a dispersion in mineral oil of barium oxide, said dispersion containing from about 0.5% to about 5.0% of methanol, reacting the said materials at a temperature of from about 20 C. to about 90 C. while retaining in the solution an amount of methanol sufiicient to carry out complete neutralization of the acid dithiophosphoric ester, and removing the oil-insoluble reaction salts by filtration.
3. Process as in claim 2, and wherein the methanol is present in an amount of from 1% to 2%.
CHARLES EARLE FUNK, JR.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS
Claims (1)
1. PROCESS FOR PREPARING A SOLUTION IN MINERAL OIL OF A HEAVY METAL SALT OF AN OIL-SOLUBLE ESTER OF DITHIOPHOSPHORIC ACID WHICH COMPRISES THE STEPS OF ADDING AN OIL-SOLUBLE ESTER OF DITHIOPHOSPHORIC ACID TO A DISPERSION IN MINERAL OIL OF A MEMBER OF THE GROUP CONSISTING OF THE OXIDE AND HYDROXIDE OF BARIUM, SAID DISPERSION CONTAINING FROM ABOUT 0.5% TO ABOUT 5.0% OF METHANOL, REACTING THE SAID MATERIALS AT A TEMPERATURE OF FROM ABOUT 20*C. TO ABOUT 90*C. WHILE RETAINING IN THE SOLUTION AN AMOUNT OF METHANOL SUFFICIENT TO CARRY OUT COMPLETE NEUTRALIZATION OF THE ACID DITHIOPHOSPHORIC ESTER, AND REMOVING THE OIL-SOLUBLE REACTION SALTS BY FILTRATION.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US2132A US2535024A (en) | 1948-01-13 | 1948-01-13 | Lubricating compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US2132A US2535024A (en) | 1948-01-13 | 1948-01-13 | Lubricating compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US2535024A true US2535024A (en) | 1950-12-26 |
Family
ID=21699359
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US2132A Expired - Lifetime US2535024A (en) | 1948-01-13 | 1948-01-13 | Lubricating compositions |
Country Status (1)
Country | Link |
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US (1) | US2535024A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2794780A (en) * | 1954-03-25 | 1957-06-04 | American Cyanamid Co | Basic zinc dialkyl dithiophosphates and methods of making the same |
US2851416A (en) * | 1956-01-30 | 1958-09-09 | Standard Oil Co | Lubricating oil composition |
US3086939A (en) * | 1961-11-13 | 1963-04-23 | Standard Oil Co | Process for neutralizing dihydrocarbon dithiophosphoric acid |
US3514476A (en) * | 1966-09-28 | 1970-05-26 | Monsanto Co | Making basic zinc double salts of o,o-dialkyl phosphorodithioic acids |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2383498A (en) * | 1943-07-10 | 1945-08-28 | Socony Vacuum Oil Co Inc | Mineral oil composition |
US2438876A (en) * | 1945-02-17 | 1948-03-30 | Socony Vacuum Oil Co Inc | Mineral oil composition |
US2466408A (en) * | 1946-01-26 | 1949-04-05 | American Cyanamid Co | Lubricating composition |
-
1948
- 1948-01-13 US US2132A patent/US2535024A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2383498A (en) * | 1943-07-10 | 1945-08-28 | Socony Vacuum Oil Co Inc | Mineral oil composition |
US2438876A (en) * | 1945-02-17 | 1948-03-30 | Socony Vacuum Oil Co Inc | Mineral oil composition |
US2466408A (en) * | 1946-01-26 | 1949-04-05 | American Cyanamid Co | Lubricating composition |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2794780A (en) * | 1954-03-25 | 1957-06-04 | American Cyanamid Co | Basic zinc dialkyl dithiophosphates and methods of making the same |
US2851416A (en) * | 1956-01-30 | 1958-09-09 | Standard Oil Co | Lubricating oil composition |
US3086939A (en) * | 1961-11-13 | 1963-04-23 | Standard Oil Co | Process for neutralizing dihydrocarbon dithiophosphoric acid |
US3514476A (en) * | 1966-09-28 | 1970-05-26 | Monsanto Co | Making basic zinc double salts of o,o-dialkyl phosphorodithioic acids |
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