US2839470A - Preparation of basic polyvalent metal salts of organic acids - Google Patents

Preparation of basic polyvalent metal salts of organic acids Download PDF

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US2839470A
US2839470A US638478A US63847857A US2839470A US 2839470 A US2839470 A US 2839470A US 638478 A US638478 A US 638478A US 63847857 A US63847857 A US 63847857A US 2839470 A US2839470 A US 2839470A
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polyvalent metal
oil
carbon dioxide
calcium
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Eleanore R Warren
Henry W Anderson
Ratner Hyman
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Shell Development Co
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Shell Development Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/62—Sulfonated fats, oils or waxes of undetermined constitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/414—Preparation of superbasic salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
    • C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G99/00—Subject matter not provided for in other groups of this subclass
    • C07G99/002—Compounds of unknown constitution containing sulfur
    • C07G99/0024—Overbased compounds
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines

Definitions

  • This invention relates to a method for preparing basic polyvalent metal salts of oil-soluble organic acids, particularly of oil-soluble petroleum sulfonic acids. More specifically, it relates to the preparation of mineral oil solutions of highly basic alkaline earth metal petroleum sulfonates.
  • alkalinity means total base number determined by electrometric titration according to ASTM designation D664-49.
  • meta1hydroxides such as Ca(OH)
  • weak salts of the same metals such as CaCO have equal alkalinity on a molefor-mole basis.
  • Sulfate ash is determined by first igniting the sample until only ash and carbon remain, then heating with sulfuric acid at 500 F.
  • polyvalent metal salts of oil-soluble organic acids can be prepared by a process comprising reacting an oil-soluble organic acid compound with a polyvalent metal carbonate which is formed in situ.
  • the process of the present invention comprises reacting, in the presence of a substantial amount of water, an oil-soluble organic acid compound, for example, an organic sulfonic acid compound, with a polyvalent metal carbonate which is formed in situ.
  • an oil-soluble organic acid compound for example, an organic sulfonic acid compound
  • the present process comprises reacting, in the presence of a substantial amount of water, an oil-soluble organic acid compound, preferably a petroleum sulfonic acid compound, with a polyvalent metal salt, preferably an alkaline earth metal salt, of carbonic acid, which salt is formed in situ from the reaction of a polyvalent metal base and carbon dioxide, at least a portion of the polyvalent metal base which reacts with the carbon dioxide being in its free state, that is, in its non-complexed state.
  • an oil-soluble organic acid compound preferably a petroleum sulfonic acid compound
  • a polyvalent metal salt preferably an alkaline earth metal salt
  • a mineral oil solution of oil-soluble, highly basic alkaline earth metal, such as calcium, petroleum sulfonates is prepared by a process comprising admixing with a mineral oil solution of an oil-soluble petroleum sulfonic acid compound, a. substantial proportion of water and a substantial proportion of an alkaline earth metal base, and adding carbon dioxide to the resulting admixture.
  • the present process comprises admixing, at an elevated temperature, for example, at a temperature of from about F. to about 250 F., preferably from about 180 F.
  • a mineral oil solution containing from about 10% to about 50%, and preferably from about 15% to about 40%, by weight, of oil-soluble neutral or slightly basic alkaline earth metal sulfonates with an alkaline earth metal base and with at least 2%, and preferably at least 5%, by Weight, based on the oil-sulfonate starting material, of Water; adding carbon dioxide to the resulting admixture, the amount of carbon dioxide added being preferably less than the theoretical amount required to convert the added alkaline earth metal base to the corresponding alkaline earth metal carbonate; drying the resulting product, as by heating to temperatures of the order of 280-320 R, and filtering the dried product to remove suspended solids, such as excess alkaline earth metal base.
  • the carbon dioxide can be added to the reaction mixture, for example, by bubbling it through the reaction mixture or by introducing the reaction mixture into an atmosphere of carbon dioxide, Preferably, the reaction mixture is agitated vigorously during the addition of the carbon dioxide.
  • organic acid com pound includes the free organic acid as well as the salts thereof, particularly the alkali metal salts and the alkaline earth metal salts thereof.
  • any condition necessary for the formation of the neutral polyvalent metal salt must also be met.
  • a water-soluble calcium salt such as calcium chloride, should be added to the reaction mixture since the Watersoluble calcium salt is necessary in the formation of the neutral calcium petroleum sulfonate.
  • oil-soluble organic acids which can be employed in the practice of the present invention are, .for example, sulfur acids and carboxylic acids of the aliphatic and cyclic types, and the corresponding thioacids.
  • the sulfur acid compounds which can be used include sulfonic, sulfarnic, sulfinic, thiosulfonic, etc., acid compounds. Of these, the sulfonic acid compounds find par ticular application under the present invention.
  • the sulfonic acids (or salts thereof) which can be employed include the aliphatic-substituted cyclic sulfonic acids in which the aliphatic substituent or substituents contain a total of at least 12 carbon atoms, for example, alkylaryl sulfonic acids, alkylcycloaliphatic sufonic acids, and alkyl-heterocyclic sulfonic acids, and aliphatic sulfonic acids in which the aliphatic radical contains at least 12 carbon atoms, particularly long chain aliphatic sulfonic acids.
  • oil-soluble sulfonic acid compounds which can be used include: petroleum sulfonic acids; petrolatum sulfonic acids; monoand polywax substituted naphthalene sulfonic, phenol sulfonic, diphenyl ether sulfonic, diphenyl ether disulfonic, naphthalene disulfide sulfonic, naphthalene disulfide disulfonic, diphenyl amine disulfonic, diphenyl amine sulfonic, thiophene sulfonic, alpha-chloronaphthalene sulfonic acids, etc.; other substituted sulfonic acids such as cetylchlorobenzene sulfonic acids, cetylphenol sulfonic acids, cetylphenol disulfide sulfonic acids, cetylphenol monosulfide sulfonic acids, cetoxy capryl-benzene sulfonic
  • petroleum sulfonic acids is intended to cover all sulfonic acids which are derived directly from petroleum products.
  • the carboxylic acids which can be employed are the oilsoluble carbocyclic carboxylic acids, including those containing a benzenoid structure, i. e., benzene, naphthalene, etc., and an oil-solubilizing radical or radicals having a total of at least about 12 carbon atoms.
  • Such acids are the oil-soluble aliphatic substituted aromatic acids as, for example, stearylbenzoic acids, monoor polywax substituted benzoic or naphthoic acids, and particularly the long chain alkyl salicyclic acids.
  • the carbocyclic carboxylic acids also include cycloaliphatic carboxylic acids containing at least about 12 carbon atoms.
  • Such acids are the petroleum naphthenic acids, cetylcyclohexane carboxylic acids, di-lauryl decahydronaphthalene carboxylic acids, di-octylcyclopentane carboxylic acids, etc. It is also contemplated to employ the thio-carboxylic acids, that is, those carboxylic acids set out above in which one or both of the oxygen atoms of the carboxylic group are replaced by sulfur. Salts of the foregoing acids can also be used.
  • the oil-soluble organic sulfonic acid compounds are particularly applicable to the preparation of mineral oil solutions of oil-soluble, highly basic alkaline earth metal petroleum sulfonates from mineral oil solutions of sulfonic acid compounds obtained by sulfonating petroleum hydrocarbon material, particularly petroleum lubricating oil fractions. Sulfonation of the petroleum hydrocarbon material with subsequent neutralization of the free sulfonic acids with an alkali metal hydroxide, can be effected by any known method as described, for example, in the following U. S.
  • oil-soluble organic acid compound in a suitable hydrocarbon prior to conversion thereof to the highly basic polyvalent metal salt.
  • Preferred hydrocarbon solvents are mineral oil fractions having a relatively low viscosity so that subsequent filtration of the highly basic product is facilitated, and having also relatively low volatility, mainly for the reason that the resulting mineral oil concentrate of the highly basic product is generally used as an additive for lubricating oil compositions. Any lubricating oil fraction can be used. Lubricating oil fractions having a viscosity of from about to about 400 seconds Saybolt Universal at 100 F. are most suitable.
  • the concentration of the oil-soluble organic acid compound in the mineral oil solution is generally "from about 10% to about 50%, and preferably from 15% to about 40%, by weight.
  • the polyvalent metal carbonate which is employed as the basification agent in the present invention is formed in situ, generally by the reaction of a polyvalent metal base, preferably an oxide or hydroxide of an alkaline earth metal, i. e., calcium, barium, strontium, or magnesium, and carbon dioxide.
  • a polyvalent metal base preferably an oxide or hydroxide of an alkaline earth metal, i. e., calcium, barium, strontium, or magnesium
  • carbon dioxide is then added to the re sulting admixture, preferably with vigorous agitation.
  • the amount of polyvalent metal base added depends on the basicity desired in the final product.
  • the amount of polyvalent metal base should be in excess of that required to form the neutral polyvalent salt of the organic acid compound. Since the present invention is intended principally to provide a process for the preparation of basic polyvalent metal salts of the organic acids which salts are more basic than those formed merely by heating the organic acid compound with an excess ofpolyvalent metal neutralizing agent, the amount of polyvalent metal base employed in the present process should exceed that which will normally react or complex with an organic acid compound merely by heating the organic acid compound with an excess of such polyvalent metal base, which amount varies depending upon the particular organic acid compound employed.
  • the polyvalent metal base which reacts in situ with the weak inorganic acid should be in its free state, that is, in its unreacted or non-complexed state.
  • the amount of polyvalent metal base used should contain at least two equivalents of polyvalent metal toreach 'equivalent of organic acid anion.
  • the amount of base added is usually substantially higher than that desired in the product since not all of the added base is necessarily solubilized in the oil phase.
  • the amount of carbon dioxide employed preferably should not exceed the theoretical amount required to convert the added polyvalent metal base to the polyvalent metal carbonate.
  • the amount of water present in the reaction mixture should be at least about 2% by weight, for example, from about 5% to about 50% by weight, based on the oilsoluble organic acid compound starting material or, where an oil solution thereof is employed on the weight of the oil solution.
  • the water and the polyvalent metal base can be separately added to the organic acid compound starting material, or an aqueous suspension of the polyvalent metal base can be prepared and this suspension then added to the organic acid compound starting material.
  • the concentration of the base in the suspension is usually from about to about 60%, and preferably from about to about by weight.
  • the weight ratio of base to water can be as high as 9, but is preferably from about /2 to about 4.
  • the temperature at which the present process is conducted is generally between about 150 and 250 F., preferably between about 180 F. and 210 F. When the process is carried out under atmospheric pressure, the temperature should not exceed about 210 F., and preferably not exceed about 200 F. so that the water present in the reaction mixture is not completely removed before the basification reaction is complete. By carrying out the process at pressures higher than atmospheric, temperatures of as high as 250 F. can be employed. 'When the reaction product has reached the desired basicity, the reaction mixture is dried, as by heating to temperatures of 280-320 F. If desired, the dried product can be airblown. The dried product is then filtered to remove suspended solids.
  • Example I 140 grams of a mineral oil solution containing about 33 by weight of calcium petroleum mahogany sulfonates and having-a base number (mg. KOH/g. concentrate) of about 20 and a control ratio of about 2.5, was diluted with 140 grams of a lubricating oil fraction having a viscosity of about 400 SSU (Seconds Saybolt Universal) at 100 F. The base number of the diluted solution was about 10. The resulting dilute solution was admixed with 8.8 grams of calcium hydroxide which was slurried in 24 cc. of water. The admixture was heated to 200 F. and maintained at this temperature during subsequent addition of carbon dioxide.
  • a base number mg. KOH/g. concentrate
  • Carbon dioxide was introduced into the admixture, with rapid stirring, at a rate of 5.6 cc./sec. for 35 minutes.
  • the resulting product was dried by heating to 300 F. and the dried, hot product was filtered.
  • the product has a base number of 40.9, a control ratio of 5.28 and an equivalent base ratio (EBR) of 178.
  • EBR equivalent base ratio
  • Example 11 280 grams of a mineral oil solution containing about 33 by weight of oil-soluble calcium petroleum sulfonates and having a base number of about 20 and a control ratio of about 2.5, was admixed with 19.4 grams of calcium hydroxide and 48 cc. of water, and the resulting admixture was heated to 200 F. Carbon dioxide was introduced into the admixture, with rapid stirring, at a rate of 5.6 cc./sec. for 40 minutes. The product was dried at 300 F. and then filtered. The product had a base number of 90.3, a control ratio of 5.46, and an EBR. of 196.
  • Example III 298 grams of a wet mineral oil solution containing about 33% by weight of calcium petroleum sulfonates (on a mineral oil-calcium petroleum sulfonate basis) and having a base number of about 20 (on a dry basis) and a control ratio of about 2.5 (on a dry basis), was admixed with 19.4 gramsof calcium hydroxide and 33.1 cc. of water.
  • a Wet mineral oil solution of calcium petroleum sulfonates refers to a product which has not been dried and filtered.
  • the resulting admixture was heated to 200 F. Carbon dioxide was introduced into the admixture, with rapid stirring, at a rate of 5.6 cc./ sec. for 20 minutes.
  • the product was dried at 300 F. and
  • the product had a base number of 77.0, a
  • Example IV i 149 grams of a wet mineral oil solution containing about 33% by weight of calcium petroleum sulfonates having a base number of about 20 and a control ratio of about 2.5, was diluted with 140 grams of lubricatingoil distillate fraction having a viscosity of about 400 SSU at F. The base number of, the dilute solution was about 10. The dilute solution was admixed with 8.8 grams of calcium hydroxide and 14 cc. of water, and the resulting admixture was heated to 200 F. Carbon dioxide was introduced into the admixture, with rapid stirring, at a rate of 2.3 cc./sec. for 30 minutes. The product was dried at 300 F. and then filtered. The producthad a base number of 31.5, a controlcratio of 5.15 and an EBR of 167.
  • Example V Example VI 200 grams of the product of Example V was admixed with 17.6 grams of calcium hydroxide and 48 cc. of water and heated to 200 F. Carbon dioxide was introduced .into the admixture, with rapid stirring, at a rate of 5.6
  • Example VII 97 grams of the product of Example VI was admixed with 8.8 grams of calcium hydroxide and 24 cc. of water, and the resulting admixture was heated to 200 F. Carbondioxide was introduced into the admixture, with rapid stirring, at a rate of 2.3 cc./sec. for 40 minutes. The product was dried at 300 F. and then filtered. The product had a base number of 162.2, a control ratio of 7.21 and an EBR of 700.
  • Example VIII 140 grams of a mineral oil solution containing about 33% by weight of calcium petroleum sulfonates and having a base number of about 20 was admixed with 44 grams of calcium hydroxide and 120 cc. of water. The resulting admixture was heated to 200 F. Carbon dioxide was introduced into the admixture, with rapid stirring, at arate of 2.3 cc./sec. for 3 hours and 45 minutes. The product was dried at 300 F. and then filtered. The product had a base number of 147, a control ratio of 6.59 and an EBR of 400.
  • Example IX Four kilograms of a mineral oil solution containing about 16% by weight of calcium petroleum sulfonates and having a base number of about and a control ratio of about 2.5 was admixed with 3.1% by weight, based on the oil solution of calcium petroleum sulfonates, of calcium hydroxide and 4.3 by weight, based on the oil solution of calcium petroleum sulfonates, of water.
  • the resulting admixture was heated to 200 F. and sprayed into a closed vessel into a carbon dioxide atmosphere.
  • the rate of introduction of carbon dioxide into the vessel was 1.8 grams/minute, the carbon dioxide dosage being 1.8% by weight based on the oil solution of calcium petroleum sulfonates.
  • the time of carbon dioxide addition was 40 minutes. of about 5 pounds per square inch gage.
  • the resulting product was dried and filtered. The product had a base number of 47.8.
  • Example X Two'kilograms of a wet mineral oil solution containing about 33% by weight of calcium petroleum sulfonates and having a base number of about and a control ratio of about 2.5 was diluted with 2 kilograms of a lubricating oil distillate fraction having a viscosity of about 100 SSU at 100 F.
  • the base number of the dilute solution was about 10.
  • the dilute solution was admixed with 3.1% by weight, based on the dilute oil solution of calcium petroleum sulfonates, of calcium hydroxide and Example XI 400 pounds of a mineral oil solution containing about 33% by weight of calcium petroleum sulfonates and having a base number of about 20 and a control ratio of about 2.5, was diluted with 93 by weight, based on the mineral ,oil solution of calcium petroleum sulfonates, of a lubricating oil fraction having a viscosity of about 100 SSU at 100 F.
  • the base number of the diluted solution was about 10.
  • the diluted solution was admixed with 6.1% by weight of calcium hydroxide and 16.4% by weight of .water, both percentages being based on the mineral oilcalcium petroleum sulfonate starting material.
  • the resulting admixture was heated to 200 F., and 3.1% by weight, based on the starting material, of carbon dioxide was added thereto with agitation.
  • the resulting product The reaction was carried out under a pressure
  • the resulting admixture was dried and filtered.
  • the product had a base number of 42.4.
  • Example XII 400 pounds of a wet mineral oil solution containing about 3% by weight of calcium petroleum sulfonates and having a base number of about 20 and a control ratio of about 2.,5 was diluted with by weight, based on the mineral oil solution of calcium petroleum sulfonates, of a lubricating oil fraction having a viscosity of about SSU at 100 F.
  • the base number of the diluted solution was about 11.
  • the diluted solution was admixed with 10.4% by weight of calcium hydroxide and 21.7% by weight of water both percentages being based on the mineral oil-calcium petroleum sulfonate starting material.
  • the resulting admixture was heated to 200 F., and 3.9% by weight, based on the starting material, of carbon dioxide was added thereto with agitation.
  • the resulting product was dried and filtered.
  • the product had a base number of 56.
  • Example XIII grams of a mineral oil solution containing about 27% by weight of neutral barium petroleum sulfonates having a sulfate ash of 6.95% w., was diluted with 140 grams of a lubricating oil fraction having a viscosity of about 400 SSU at 100 F. The dilute solution was admixed with 36 grams of barium hydroxide and 32 cc. of water, and the resulting admixture was heated to F. Carbon dioxide was introduced into the admixture, with rapid stirring, at a rate of 5.6 cc./sec. for 2 hours. The product was dried at 300 F. and then filtered. The product had a base number of 44.7, a sulfate ash content of 13.3% w., a control ratio of 3.36 and an EBR of 232.
  • Example XIV 77 grams of a mineral oil solution containing about 60% by weight of sodium petroleum sulfonates wa diluted with 63 grams of a lubricating oil fraction having a viscosity of about 100 SSU at 100 F. and with 70 grams of a lubricating oil fraction having a viscosity of about 400 SSU at 100 F.
  • the resulting solution was admixed with 17.6 grams of calcium hydroxide, 7.1 grams of calcium chloride and 48 cc. of water, and the resulting admixture was heated to 200 F. Carbon dioxide was introduced into the admixture, with rapid stirring, at a rate of 5.6 cc./sec. for 2 hours.
  • the product was dried at 300 F. and then filtered.
  • the resulting mineral oil solution of basic calcium petroleum sulfonates had a base number of 46.25, a sulfate ash con tent of 10.2% w., a control ratio of 4.53 and an EBR of 122.
  • the basification agent that is, the polyvalent metal salt of a weak inorganic acid
  • Example XVI 140 grams of a mineral oil solution containing about 33% by weight of calcium petroleum sulfonates and having a base number of about 20 was diluted with 140 grams
  • the base number of the resulting dilute solution was about 10. Five cc. of water was added to the resulting dilute solution, and carbon dioxide was introduced thereinto, with rapid stirring, at a very high rate for 20 minutes at 190 F. Then 11.9 grams of calcium carbonate in 10 cc. of water was added to the resulting mixture, and stirring was continued for 1 hour at 190 F.
  • the resulting product was dried at 300 F. and then filtered.
  • the product had a base number of 10. r r
  • the amount of water present in the reaction mixture should be at least about 2% by weight, and preferably at least about 5% by weight, based on the organic acid compound starting material.
  • the following example illustrates the fact that virtually no increase in basicity of the starting material can be obtained in the absence of water.
  • Example XVIII A mineral oil solution containing about 16% by weight of calcium petroleum sultonates and having a base number of about 10, was admixed with 3.1% by weight, based on the oil solution of calcium petroleum sulfonates, of calcium hydroxide, and the resulting admixture was heated to 200 F. Carbon dioxide was introduced into the admixture, Withrapid stirring, at a rate of 1 gram/ minute, the carbon dioxide dosage being 1.3% by weight, based on oil solution of calcium petroleum sulfonates. The resulting product was dried at 300 F. and then filtered. The product had a base number of 11.0. Thus the basicity of the starting material was increased by only about one unit.
  • the oil 1003 grams of this product were mixed with 501 grams of a high viscosity index lubricating oil fraction having mixture, whereby a mineral oil solution of barium 10 a viscosity of about 100 SSU (Seconds SayboltUnivetsal) at 100 F., 144 grams of calcium hydroxide and 234 milliliters of water. This mixture was heated to 200 F. and stirred continuously. Carbon dioxide was bubbled into the mixture at the rate of 0.7 gram per minute for minutes. The mixture was then dried at 300 F. and filtered.
  • the product was an oil solution of the highly basic calcium salt of the naphthenic acids; it had a base number of 59.1, a sulfated ash of 7.18% and an EBR of 230.
  • the highly basic products in accordancewith the present invention are particularly useful as addition agents for lubricating oils.
  • a method for increasing the basicity of a mineral oil solution of calcium petroleum sulfonates which comprises admixing said mineral oil solution containing at least 10% by Weight of calcium, petroleum sulfonates, said sulfonates being the only chemically reactive organic compounds present in said solution, with an aqueous suspension containing a substantial amount of calcium hydroxide, the weight of water in said suspension being at least equal to 2% of the weight of said mineral oil solution, and adding carbon dioxide to. the resulting admixture, whereby a mineral oil solution of calcium petroleum sulfonates of increased'basicity is obtained.
  • a method for increasing the basicity of a mineral oil solution of barium petroleum sulfonates which comprises admixing said mineral oil solution containing at least 10% by weight of barium petroleum sulfonates, said sulfonates being the only chemically reactive organic compounds present in said solution, with an aqueous suspension containing a substantial amount of barium hydroxide, the weight of water in said suspension being at least equal to 2% of the weight of saidmineral oil solution, and adding carbon dioxide to the resulting adpetroleum sulfonates of increased basicity is obtained.
  • a method for preparing a mineral oil solution of oil-soluble, highlybasic calcium petroleum sulfonates which comprises admixing. a mineral oil solution containing at least 10% by weight of sodium petroleum sulfonates, said sulfonates being the only chemically reactive organic compounds present in said solution, with an amount of calcium chloride sufficient to convert said sodium petroleum sulfonates to neutral calcium petroleum sulfonates, a substantial amount of calcium hydroxide and a weight of water equal to at least 2% of the weight of such mineral oil solution, and adding carbon dioxide to the resulting admixture, whereby a mineral oil solution of oil-soluble, highly basic calcium petroleum sulfonates is obtained.
  • a method for increasing the basicity of a mineral oil solution of calcium alkyl salicylates in which the alkyl group contains at least 12 carbon atoms which comprises admixing said mineral oil solution containing at least by weight of calcium alkyl salicylates, said salicylates be ing the only chemically reactive organic compounds present in said solution, with an aqueous suspension containing a substantial amount of calcium hydroxide, the weight of water in said suspension being at least equal to 2% of the weight of said mineral oil solution, and adding carbon dioxide to the resulting admixture, whereby a mineral oil solution of calcium alkyl salicylates of increased basicity is obtained.
  • a method for increasing the basicity of a mineral oil solution of alkaline earth metal petroleum sulfonates which comprises admixing said mineral oil solution containing at least 10% by weight of alkaline earth metal petroleum sulfonates, said sulfonates being the only chemically reactive organic compounds present in said solution, with a weight of water equal to at least 2% of the weight of such mineral oil solution and with a substantial amount of an alkaline earth metal base, and adding carbon dioxide to the resulting admixture, whereby a mineral oil solution of alkaline earth metal petroleum sulfonates of increased basicity is obtained.
  • a method for preparing a mineral oil solution of oil-soluble, highly basic alkaline earth metal petroleum sulfonates which comprises admixing a mineral oil solution containing at least 10% by weight of alkali metal petroleum sulfonates, said sulfonates being the only chemically reactive organic compounds present in said solution, with an amount of a water-soluble alkaline earth metal salt sufiicient to convert said alkali metal petroleum sulfonates to neutral alkaline earth metal petroleum sulfonates, a substantial amount of an alkaline earth metal base and a weight of water equal to at least 2% of the weight of such mineral oil solution, and adding carbon dioxide to the resulting admixture, whereby a mineral oil solution of oil-soluble, highly basic alkaline earth petroleum sulfonates is obtained.
  • anoil-soluble, highly basic polyvalent metal salt of a petroleum sulfonic acid comprising reacting an oil-soluble petroleum sulfonic acid compound, as the only reactive organic compound, in the presence of a weight of water equal to at least 2% of the weight of said sulfonic acid compound, with a polyvalent metal carbonate which is formed in situ by the reaction of a polyvalent metal base and carbon dioxide, at least a portion of said polyvalent metal base being in the free state.
  • a method for preparing an oil-soluble, highly basic polyvalent metal salt of an alkyl salicylic acid in which the alkyl radical contains at least 12 carbon atoms comprising mixing an oil-soluble alkyl salicylic acid compound in which the alkyl radical contains at least 12 carbon atoms, as the only reactive organic compound, with a weight of water equal to at least 2% of the weight of such salicylic acid compound and with a substantial amount of a polyvalent metal base, and adding carbon dioxide to the resulting mixture.
  • an oil-soluble, highly basic polyvalent metal salt of an alkyl salicylic acid comprising reacting an oil-soluble alkyl salicylic acid compound in which the alkyl group contains at least 12 carbon atoms, as the only reactive organic compound, in the presence of a weight of water equal to at least 2% of the weight of said salicylic acid compound, with a polyvalent metal carbonate which is formed in situ by the reaction of a polyvalent metal base and carbon dioxide, at least a portion of said polyvalent metal base being in the free state.
  • a method for preparing an oil-soluble, highly basic polyvalent metal salt of a petroleum naphthenic acid comprising reacting an oil-soluble petroleum naphthenic acid compound, as the only reactive organic compound, in the presence of a weight of water equal to at least 2% of the weight of said naphthenic acid compound, with a polyvalent metal carbonate which is formed in situ by the reaction of a polyvalent metal base and carbon dioxide, at least a portion of said polyvalent metal base being in the free state.
  • a method for preparing oil-soluble, highly basic alkaline earth metal petroleum naphthenates comprising mixing an oil-soluble petroleum naphthenic acid compound, as the only reactive organic compound, with a weight of water equal to at least 2% of the weight of such naphtheni'c acid compound and with a substantial amount of an alkaline earth metal base, and adding carbon dioxide to the resulting mixture.
  • a method for increasing the basicity of a mineral oil solution of alkaline earth metal petroleum naphthenates which comprises admixing said mineral oil solution containing at least 10% by Weight of alkaline earth metal petroleum naphthenates, said naphthenates being the only chemically reactive organic compounds present in said solution, with a weight of water equal to at least 2% of the weight of such mineral oil solution and with a substantial amount of an alkaline earth metal base, and adding carbon dioxide to the resulting admixture, whereby a mineral oil solution of alkaline earth metal petroleum naphthenates of increased basicity is obtained.
  • an oil-soluble polyvalent metal salt of an organic acid comprising reacting, as the only chemically reactive organic material, an oil-soluble organic acid compound containing at least 12 carbon atoms and selected from the class consisting of (1) the petroleum sulfonic acids, (2) carbocyclic carboxylic acids and (3) salts of these acids with alkali metals and with alkaline earth metals, in the presence of a substantial aqueous phase comprising a weight of water equal to not less than 2% of the weight of said organic acid compound, with apolyvalent metal carbonate which is formed in situ by the reaction of a polyvalent metal base and carbon dioxide, at least a part of said polyvalent metal base being in the free state.
  • an oil-soluble polyvalent metal salt of an organic acid comprising reacting a hydrocarbon oil solution containing as the only chemically reactive organic material, at least 10% by weight of an oil-soluble organic acid compound containing at least 12 carbon atoms and selected from the class consisting of (1) petroleum sulfonic acids, (2) carbocyclic carboxylic acids and (3) salts of these acids with alkali metals and with alkaline earth metals, in the presence of a substantial aqueous phase comprising a Weight of Water equal to not less than 2% of the weight of said oil solution, with a polyvalent metal carbonate which is formed in situ by the reaction of a polyvalent metal base and carbon dioxide, at least a part of said polyvalent metal base being in the free state.
  • an oil-soluble polyvalent metal salt of an organic acid comprising mixing a hydrocarbon oil solution containing as the only chemically reactive organic material at least 10% by weight of an oil-soluble organic acid compound containing at least 12 carbon atoms per molecule and selected from the class consisting of (l) petroleum sulfonic acids, (2) carbocyclic carboxylic acids and (3) salts of these acids with alkali metals and with alkaline earth metals with a 14 weight of water equal to at least 2% of the weight of said oil solution, and a substantial amount of a polyvalent metal base, and adding carbon dioxide to the resulting mixture, said aqueous phase being maintained throughout the addition of carbon dioxide.
  • a hydrocarbon oil solution containing as the only chemically reactive organic material at least 10% by weight of an oil-soluble organic acid compound containing at least 12 carbon atoms per molecule and selected from the class consisting of (l) petroleum sulfonic acids, (2) carbocyclic carboxylic acids and (3) salts of these acids with alkali metals and with alkaline earth
  • a hydrocarbon oil solution containing as the only chemically reactive organic material at least 16% by Weight of an oil-soluble organic acid compound containing at least 12 carbon atoms per molecule and selected from the class consisting of (l) petroleum sulfonic acids, (2) carbocyclic carboxylic acids and (3) salts of these acids with alkali metals and with alkaline earth metals with a weight of Water equal to at least 2% of the Weight of said oil solution, and a substantial amount of an alkaline earth metal base, and adding carbon dioxide to the resulting mixture, said aqueous phase being maintained throughout the addition of carbon dioxide.

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Cited By (38)

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US2930757A (en) * 1957-10-16 1960-03-29 Exxon Research Engineering Co Lubricating compositions containing salts of monocarboxylic acids and free alkalinity
US2958662A (en) * 1955-09-26 1960-11-01 Shell Oil Co Detergent and wear inhibiting mineral oil compositions
US2958660A (en) * 1955-09-26 1960-11-01 Shell Oil Co Detergent and wear inhibiting mineral lubricating oil compositions
US3012965A (en) * 1957-06-07 1961-12-12 Continental Oil Co Method of preparing a stable dispersion of an inorganic compound in a lubricating oil
US3014866A (en) * 1958-12-29 1961-12-26 California Research Corp Lubricating oil compositions
US3046224A (en) * 1957-06-10 1962-07-24 Socony Mobil Oil Co Inc High barium content complex salts of sulfonic acids and petroleum fractions containing the same
US3050464A (en) * 1959-04-01 1962-08-21 Universal Oil Prod Co Detergent-containing lubricating oil
US3052529A (en) * 1953-05-28 1962-09-04 Ethyl Corp Stabilized hydrocarbon fuels and lubricants
US3242079A (en) * 1962-04-06 1966-03-22 Lubrizol Corp Basic metal-containing thickened oil compositions
US3281356A (en) * 1963-05-17 1966-10-25 Lubrizol Corp Thermally stable water-in-oil emulsions
US3321405A (en) * 1962-11-19 1967-05-23 Monsanto Co Functional fluid compositions containing tetrahydrofurfuryl meth-acrylate
US3368971A (en) * 1965-11-22 1968-02-13 Ethyl Corp Lubricating oil compositions
DE1268767B (de) * 1963-01-14 1968-05-22 Bray Oil Co Verfahren zur Herstellung von kolloidalen Dispersionen von Carbonaten von Metallen der XI. Gruppe des Periodischen Systems in Schmieroelen
US3471403A (en) * 1967-03-07 1969-10-07 Lubrizol Corp Basic metal carboxylate complex
US3523899A (en) * 1966-04-04 1970-08-11 Phillips Petroleum Co Overbased metal petroleum sulfonate and method for its preparation
US3523898A (en) * 1966-04-05 1970-08-11 Phillips Petroleum Co Increased base number metal petroleum sulfonate and process for its preparation
US3523897A (en) * 1966-04-05 1970-08-11 Phillips Petroleum Co Increased base number metal petroleum sulfonate and process for its preparation
US3625893A (en) * 1967-11-06 1971-12-07 Shell Oil Co Lubricating compositions having improved oxidation stability and antirust properties
US3764571A (en) * 1971-02-18 1973-10-09 Dart Ind Inc Organotin stabilizer systems
US3865737A (en) * 1973-07-02 1975-02-11 Continental Oil Co Process for preparing highly-basic, magnesium-containing dispersion
US3997456A (en) * 1972-11-06 1976-12-14 Bell & Howell Company Wide latitude toner
US4055419A (en) * 1974-10-11 1977-10-25 Bell & Howell Company Method of developing electrostatic images using wide latitude toner
US4065396A (en) * 1970-02-09 1977-12-27 Bray Oil Co. Magnesium oxide process
US4129589A (en) * 1976-07-15 1978-12-12 Surpass Chemicals Limited Over-based magnesium salts of sulphonic acids
EP0011069A1 (en) * 1978-11-14 1980-05-28 Surpass Chemicals Limited Process for preparing overbased oil soluble magnesium salts
US4385008A (en) * 1979-10-18 1983-05-24 Interox Chemicals Limited Bleaching agent
US20080064616A1 (en) * 2004-10-25 2008-03-13 Huntsman Petrochemical Corporation Fuel And Oil Detergents
US9273265B2 (en) 2011-10-31 2016-03-01 Nch Corporation Calcium carbonate based sulfonate grease compositions and method of manufacture
US9458406B2 (en) 2011-10-31 2016-10-04 Nch Corporation Calcium hydroxyapatite based sulfonate grease compositions and method of manufacture
US9976102B2 (en) 2011-10-31 2018-05-22 Nch Corporation Composition and method of manufacturing calcium sulfonate greases using alkali metal hydroxide and delayed addition of non-aqueous converting agents
US9976101B2 (en) 2011-10-31 2018-05-22 Nch Corporation Method of manufacturing calcium sulfonate greases using delayed addition of non-aqueous converting agents
US10087391B2 (en) 2016-05-18 2018-10-02 Nch Corporation Composition and method of manufacturing calcium magnesium sulfonate greases without a conventional non-aqueous converting agent
US10087388B2 (en) 2016-05-18 2018-10-02 Nch Corporation Composition and method of manufacturing calcium sulfonate and calcium magnesium sulfonate greases using a delay after addition of facilitating acid
US10087387B2 (en) 2016-05-18 2018-10-02 Nch Corporation Composition and method of manufacturing calcium magnesium sulfonate greases
US10392577B2 (en) 2016-05-18 2019-08-27 Nch Corporation Composition and method of manufacturing overbased sulfonate modified lithium carboxylate grease
US10519393B2 (en) 2016-05-18 2019-12-31 Nch Corporation Composition and method of manufacturing calcium magnesium sulfonate greases
US11661563B2 (en) 2020-02-11 2023-05-30 Nch Corporation Composition and method of manufacturing and using extremely rheopectic sulfonate-based greases
US12331261B2 (en) 2018-11-20 2025-06-17 Nch Corporation Composition and method of manufacturing sulfonate-based greases using a glycerol derivative

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DE1259879B (de) * 1960-05-21 1968-02-01 Exxon Research Engineering Co Verfahren zur Herstellung von Schmieroelzusaetzen mit hoher Alkalitaet auf der Basisvon Erdalkalisulfonaten

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US2501732A (en) * 1946-10-14 1950-03-28 Union Oil Co Modified lubricating oil
US2616924A (en) * 1951-03-16 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes and method of making same
US2619460A (en) * 1949-03-26 1952-11-25 Union Oil Co Lubricating oil composition
US2695910A (en) * 1951-05-03 1954-11-30 Lubrizol Corp Methods of preparation of superbased salts

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US2501732A (en) * 1946-10-14 1950-03-28 Union Oil Co Modified lubricating oil
US2619460A (en) * 1949-03-26 1952-11-25 Union Oil Co Lubricating oil composition
US2616924A (en) * 1951-03-16 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes and method of making same
US2695910A (en) * 1951-05-03 1954-11-30 Lubrizol Corp Methods of preparation of superbased salts

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3052529A (en) * 1953-05-28 1962-09-04 Ethyl Corp Stabilized hydrocarbon fuels and lubricants
US2958662A (en) * 1955-09-26 1960-11-01 Shell Oil Co Detergent and wear inhibiting mineral oil compositions
US2958660A (en) * 1955-09-26 1960-11-01 Shell Oil Co Detergent and wear inhibiting mineral lubricating oil compositions
US3012965A (en) * 1957-06-07 1961-12-12 Continental Oil Co Method of preparing a stable dispersion of an inorganic compound in a lubricating oil
US3046224A (en) * 1957-06-10 1962-07-24 Socony Mobil Oil Co Inc High barium content complex salts of sulfonic acids and petroleum fractions containing the same
US2930757A (en) * 1957-10-16 1960-03-29 Exxon Research Engineering Co Lubricating compositions containing salts of monocarboxylic acids and free alkalinity
US3014866A (en) * 1958-12-29 1961-12-26 California Research Corp Lubricating oil compositions
US3050464A (en) * 1959-04-01 1962-08-21 Universal Oil Prod Co Detergent-containing lubricating oil
US3242079A (en) * 1962-04-06 1966-03-22 Lubrizol Corp Basic metal-containing thickened oil compositions
US3321405A (en) * 1962-11-19 1967-05-23 Monsanto Co Functional fluid compositions containing tetrahydrofurfuryl meth-acrylate
DE1268767B (de) * 1963-01-14 1968-05-22 Bray Oil Co Verfahren zur Herstellung von kolloidalen Dispersionen von Carbonaten von Metallen der XI. Gruppe des Periodischen Systems in Schmieroelen
US3281356A (en) * 1963-05-17 1966-10-25 Lubrizol Corp Thermally stable water-in-oil emulsions
US3368971A (en) * 1965-11-22 1968-02-13 Ethyl Corp Lubricating oil compositions
US3523899A (en) * 1966-04-04 1970-08-11 Phillips Petroleum Co Overbased metal petroleum sulfonate and method for its preparation
US3523898A (en) * 1966-04-05 1970-08-11 Phillips Petroleum Co Increased base number metal petroleum sulfonate and process for its preparation
US3523897A (en) * 1966-04-05 1970-08-11 Phillips Petroleum Co Increased base number metal petroleum sulfonate and process for its preparation
US3471403A (en) * 1967-03-07 1969-10-07 Lubrizol Corp Basic metal carboxylate complex
US3625893A (en) * 1967-11-06 1971-12-07 Shell Oil Co Lubricating compositions having improved oxidation stability and antirust properties
US4065396A (en) * 1970-02-09 1977-12-27 Bray Oil Co. Magnesium oxide process
US3764571A (en) * 1971-02-18 1973-10-09 Dart Ind Inc Organotin stabilizer systems
US3997456A (en) * 1972-11-06 1976-12-14 Bell & Howell Company Wide latitude toner
US3865737A (en) * 1973-07-02 1975-02-11 Continental Oil Co Process for preparing highly-basic, magnesium-containing dispersion
US4055419A (en) * 1974-10-11 1977-10-25 Bell & Howell Company Method of developing electrostatic images using wide latitude toner
US4129589A (en) * 1976-07-15 1978-12-12 Surpass Chemicals Limited Over-based magnesium salts of sulphonic acids
EP0011069A1 (en) * 1978-11-14 1980-05-28 Surpass Chemicals Limited Process for preparing overbased oil soluble magnesium salts
US4385008A (en) * 1979-10-18 1983-05-24 Interox Chemicals Limited Bleaching agent
US4403994A (en) * 1979-10-18 1983-09-13 Interox Chemicals Limited Bleaching agents
US20080064616A1 (en) * 2004-10-25 2008-03-13 Huntsman Petrochemical Corporation Fuel And Oil Detergents
US9976101B2 (en) 2011-10-31 2018-05-22 Nch Corporation Method of manufacturing calcium sulfonate greases using delayed addition of non-aqueous converting agents
US11072756B2 (en) 2011-10-31 2021-07-27 Nch Corporation Calcium hydroxyapatite based calcium sulfonate grease compositions and method of manufacture
US9976102B2 (en) 2011-10-31 2018-05-22 Nch Corporation Composition and method of manufacturing calcium sulfonate greases using alkali metal hydroxide and delayed addition of non-aqueous converting agents
US9273265B2 (en) 2011-10-31 2016-03-01 Nch Corporation Calcium carbonate based sulfonate grease compositions and method of manufacture
US9458406B2 (en) 2011-10-31 2016-10-04 Nch Corporation Calcium hydroxyapatite based sulfonate grease compositions and method of manufacture
US10316266B2 (en) 2011-10-31 2019-06-11 Nch Corporation Calcium hydroxyapatite based calcium sulfonate grease compositions and method of manufacture
US10087387B2 (en) 2016-05-18 2018-10-02 Nch Corporation Composition and method of manufacturing calcium magnesium sulfonate greases
US10087388B2 (en) 2016-05-18 2018-10-02 Nch Corporation Composition and method of manufacturing calcium sulfonate and calcium magnesium sulfonate greases using a delay after addition of facilitating acid
US10392577B2 (en) 2016-05-18 2019-08-27 Nch Corporation Composition and method of manufacturing overbased sulfonate modified lithium carboxylate grease
US10519393B2 (en) 2016-05-18 2019-12-31 Nch Corporation Composition and method of manufacturing calcium magnesium sulfonate greases
US10087391B2 (en) 2016-05-18 2018-10-02 Nch Corporation Composition and method of manufacturing calcium magnesium sulfonate greases without a conventional non-aqueous converting agent
US11168277B2 (en) 2016-05-18 2021-11-09 Nch Corporation Composition and method of manufacturing calcium magnesium sulfonate greases
US12031100B2 (en) 2016-05-18 2024-07-09 Nch Corporation Composition and method of manufacturing calcium magnesium sulfonate greases
US12331261B2 (en) 2018-11-20 2025-06-17 Nch Corporation Composition and method of manufacturing sulfonate-based greases using a glycerol derivative
US11661563B2 (en) 2020-02-11 2023-05-30 Nch Corporation Composition and method of manufacturing and using extremely rheopectic sulfonate-based greases
US12146114B2 (en) 2020-02-11 2024-11-19 Nch Corporation Composition and method of manufacturing and using extremely rheopectic sulfonate-based greases

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