US3755170A - Preparation of highly basic alkylphenates and sulfurized alkyphenates - Google Patents

Preparation of highly basic alkylphenates and sulfurized alkyphenates Download PDF

Info

Publication number
US3755170A
US3755170A US00148262A US3755170DA US3755170A US 3755170 A US3755170 A US 3755170A US 00148262 A US00148262 A US 00148262A US 3755170D A US3755170D A US 3755170DA US 3755170 A US3755170 A US 3755170A
Authority
US
United States
Prior art keywords
alkylphenol
oil
parts
sulfurized
admixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00148262A
Other languages
English (en)
Inventor
L Rogers
M Hunt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ConocoPhillips Co
Original Assignee
Continental Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Continental Oil Co filed Critical Continental Oil Co
Application granted granted Critical
Publication of US3755170A publication Critical patent/US3755170A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/502—Oil-based compositions
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic 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
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid 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
    • C10M2207/40—Fatty vegetable or animal oils
    • 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
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing 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
    • 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
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
    • 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
    • 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
    • C10M2223/042—Metal salts thereof
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • ABSTRACT Process for preparing highly basic alkaline earth metal alkylphenates or sulfurized alkylphenates wherein the process comprises:
  • highly basic alkaline earth metal salts of alkylphenates or sulfurized alkylphenates as additives in lubricating oils has been known for several years.
  • highly basic refers to materials containing an excess of alkaline earthmetal basic compounds over the amount of alkaline earth-metal required to neutralize the alkylphenol or sulfurized alkylphenol.
  • the presence of these, basic alkalineearth metal compounds serves to neutralize acidic cmpounds formed during combustion of the fuel used.
  • the present invention is concerned with'an improved 2 3,350,310; 3,367,867; 3,372,l l6; and 3,474,035. Inasmuch as the latter-mentioned patents are considered to be even less pertinent than the ones discussed, it is not believed necessary to provide any discussion of them herein.
  • the present invention concerns a pro cessfor preparing highly basic magnesium, calcium or barium salts of alkylphenols or sulfurized alkylphenols, wherein the process comprises the steps of:
  • step (b) adding to the admixture of step (a) an overbasing amountof magnesium, calcium or barium in a glycol ether at a temperature of to about 55 C.,
  • U.S. Pat. No. 2,788,325 teaches the use ofmagnesium alkoxy alkoxides to prepare neutral magnesium phenates. The patent teaches the use of temperatures between 100 C. and 250 C. and-substantially anhydrous conditions.
  • US. Pat. No. 2,808,377 teaches a process for preparing neutralized alkaline earth metal alkylphenolsultides. The process uses a pre-treatmentstep wherein from 3 to 5 percent of the amount of alkaline earth metal base required to neutralize the alkylphenol sulfide is used. The temperature in the pre-treatment step is ll60 F. (54-7l C.).
  • an important feature of the process of the present invention is that from about 1 to about 2.5 moles of water, per mole of dispersed basic alkaline earth metal compound in the product, must be present prior to the addition of any of the alkaline earth metal.
  • step (b) adding to the admixture of step (b) a neutralizing amount of magnesium, calcium or barium in a glycol ether at a temperature higher than that of step (b) and in the range of about 55 to about C., and
  • R is a straight chain or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from four to 30 carbon atoms, preferably from nine to 15 carbon atoms, and n is an integer having a value of l or 2.
  • the total number of carbon atoms for the alkyl groups has a minimum value of 8 and a maximum value of 40. Thus, when n is l the minimum number of carbon atoms in R is 8.
  • hydrocarbon radicals examples include alkyl radicals such as butyl, hexyl, octyl, nonyl, decyl, dodecyl, hexcdecyl, eicosyl, hexacosyl and triacontyl; radicals derived from petroleum hydrocarbons such as white oil, wax and olefin polymers (e.g. polypropylene and polybutylene).
  • Suitable sulfurized alkylphenols include those materials prepared by sulfurizing alkylphenols using any of the known methods. For example, it is known that sulfur monochloride can be used to prepare sulfurized alkylphenols. Such a method is described in US. Pat. No. 2,409,687.
  • the sulfurized alkylphenols which are suitable in our process can be illustrated by materials represented by the following formula:
  • OH OH gengmm R(n) wherein m is a number in the range of 1 to 3, more usually in the range of l to 2, and R and n are as described in the preceding description of the alkylphenols. It is to be understood that the preceding description is typical of the sulfurized alkylphenols which can be used and that our process is not limited to materials having the formula shown in the foregoing.
  • the sulfurized alkylphenols which are useful in our process suitably contain from about 2 to about 14 percent by weight sulfur.
  • the amount of sulfur is from about 4 to about 12 percent by weight.
  • nonvolatile diluent oils are suitable in the process of our invention since the principle requisites for these materials are that they function as a solvent for the alkylphenate or sulfurized alkylphenate and serve to reduce the viscosity of the final product mixture. Often a small amount of the nonvolatile diluent oil is present in conjunction with the alkylphenol or sulfurized alkylphenol used in the process.
  • the nonvolatile diluent oils have a boiling point in excess of about 200 C.
  • nonvolatile diluent oils examples include mineral lubricating oils obtained by conventional refining procedures, synthetic lubricating oils such as polymers or propylene, polyoxyalkalenes, polyoxypropylene; dicarboxylic acid esters, and esters of acids or phosphorus; synthetic hydrocarbon lubricating oils, such as di-n-alkylbenzenes and oligomers of C -C alpha-olefins; vegetable oils, such as corn oil, cottonseed oil, and castor oil; animal oils, such as lard oil and sperm oil. Mixtures of these materials can also be employed as the nonvolatile diluent.
  • nonvolatile diluent oils the mineral lubricating oils and the synthetic lubricating oils are considered more suitable, with the mineral lubricating oils being preferred.
  • Suitable process solvents for use in our process have a boiling point below about 150 C.
  • suitable volatile process solvents include aromatic hydrocarbons, such as benzene, toluene, xylene, aliphatic hydrocarbons, such as hexane, heptane, petroleum naphtha, glycol ethers, as defined hereinafter, and primary aliphatic C,C alcohols.
  • the suitable alkaline earth metals both for neutralizing the alkylphenol or sulfurized alkylphenol and for forming the dispersed basic compound, are magnesium, calcium or barium. Of these materials calcium and magnesium are considered more suitable, with.
  • Suitable glycol ethers for use in our process include monoethers of ethylene glycol and monoethers of diethylene glycol containing up to eight carbon atoms.
  • Preferred glycol ethers are the monoethyl ether of ethylene glycol and the monomethyl ether of ethylene glycol. These materials are available commercially under the trademarks Cellosolve and methyl Cellosolve.
  • the monomethyl ether of diethylene glycol is available commercially under the trademark Carbitol.
  • the monoethers of ethylene glycol are also known as alkoxy alkanols, and more specifically as alkoxy ethanols. These materials have the generic formula ROCH,CH,OH
  • the monoether of diethylene glycol has the generic formula HOCH,CH,OCH,CH,OR, where R is a C to C alkyl group.
  • the metal used in the process is present as a solution in the suitable glycol ether.
  • a carbonated metal alkoxide The preparation of a calcium alkoxide-carbonate in an alkoxy alkanol solvent is described in U.S. Pat. No. 3,150,088. Similarly, the preparation of the magnesium analog is described in U.S. Pat. No. 3,150,089.
  • the glycol ether solution of the metal contains from about 1 to about 30 weight percent, preferably from about 5 to about 25 weight percent of the metal. 0
  • the water requirements of the process of our invention can be met using water per se or a glycol etherwater mixture.
  • an oil-soluble sulfonic acid in the process of our invention.
  • the amount of oil-soluble sulfonic acid is from about 0.1 to about 50 parts per parts of alkylphenol or sulfurized alkylphenol.
  • oil-soluble sulfonic acid When using the oil-soluble sulfonic acid preferably a volatile hydrocarbon solvent (elg. hexane) containing the oil-soluble sulfonic acid is used.
  • oilsoluble sulfonic acid is well known in the art. In general, it refers to materials wherein the hydrocarbon portion of the molecule has a molecular weight in the range of about 300 to about 1,000, preferably in the range of about 370 to about 700.
  • Particularly suitable oil-soluble sulfonic acids are those prepared from various synthetic hydrocarbon sulfonation feedstocks. These materials are usually alkylbenzenes being either monoor dialkyl substituted. The alkyl groups have sufficient carbon atoms to attain the requisite molecular weight range described in the foregoing.
  • Nonvolatile diluent oil lS-95 20-90 Water 0.20l4.0 0.30-l0.00 Glycol ether solution of magnesium containing: Magnesium 0.40l0.0 0.8-9.0 Glycol ether 2.0-1000 3.0200.0
  • PROCESS CONDITIONS In conducting the process of our invention, there is first formed an admixture, in a suitable reaction vessel of the alkylphenol or sulfurized alkylphenol, nonvolatile diluent oil, volatile process solvent and water. In those cases where it is desired to use an oil-soluble sulfonic acid, this material is added to the admixture at this point.
  • an overbasing amount (from about 0.10 to 5 equivalents per equivalent of alkylphenol or sulfurized alkylphenol) of alkaline earth metal in a glycol ether.
  • the overbasing amount of the alkaline earth metal in the glycol ether is added while maintaining the temperature of the admixture in the range of about to about 55 C. While the time of adding the overbasing amount of the alkaline earth metal in a glycol ether is not particularly critical, it is desirable that this addition occurs in a time period of from about 5 to about 120 minutes, preferably from about 30 to about 90 minutes. In this connection it is our hypothesis that since neutralization of alkylphenols requires higher temperatures that no, or at least very little, neutralization of the alkylphenol occurs under the conditions under which this step is conducted.
  • the dispersoid alkaline earth metal basic compound be a hydroxide
  • the dispersoid alkaline earth metal basic compound be a carbonate
  • a neutralizing amount of the desired alkaline ea metal in a glycol ether is then added to the admixture.
  • this step is conducted while maintaining the temperature higher than in the overbasing step and in the range of about 55 to about 100 C.
  • the admixture is then heated to a suitable temperature (e.g., about 150 C.) to remove the volatile materials. If it is desirable that the dispersoid material be an alkaline earth metal carbonate, the admixture can be blown with CO during the final heating step. Blowingwith CO at this point serves to substantially complete the carbonation of the alkaline earth metal compound and to remove traces of volatile materials.
  • a suitable temperature e.g., about 150 C.
  • an additional amount of a nonvolatile diluent oil can be added at this point.
  • the dispersed metal compound As the base number" which refers to milligrams of potassium hydroxide per gram of sample.
  • the base number is an acetic base number referring to an acetic acid titration method which utilizes glacial acetic acid and a solution of perchloric acid in glacial acetic acid as the titrant.
  • a second method uses the term metal ratio which is defined as the ratio of excess equivalents of metal in the composition to the equivalents of metal theoretically combinable as a normal salt with the alkylphenol or sulfurized alkylphenol. 1
  • the products of our invention suitably have a metal ratio in the range of about 0.05 to about 5.0, preferably in the range of about 0.4 to about 2.0.
  • EXAMPLE I This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium alkylphenate.
  • the water was present in a water/methoxy ethanol azeotrope containing 50 percent water. This material contained 7.6 percent magnesium.
  • the product had a very slight haze which was easily removed by filtering through a filter funnel precoated with Hyflo (a diatomaceous earth filter acid).
  • the product had an acetic base number of 236 (theoretical 225) and a metal ratio of 1.03.
  • EXAMPLE 2 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium salt of a sulfurized alkylphenate.
  • the product was a bright, clear, oi1-soluble material having an acetic base number of 175 (theoretical 180) and a metal ratio of 0.88.
  • EXAMPLE 3 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium alkylphenate.
  • This material was an admixture of 70 grams of methoxy ethanol and 212 grams of a methoxy ethanol solution of magnesium methoxy ethoxide-carbonate complex containing 7.6 percent calcium.
  • the product had an acetic base number of 251 (theoretical 250) and a metal ratio of 1.49.
  • EXAMPLE 4 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium alkylphenate. It differs from Example 3 primarily in that a different type of alkylphenate was used.
  • EXAMPLE This example illustrates the preparation of a dispersion of magnesium carbonate in a sulfurizedalkylphe- 60 rcent alkylbenzenes as described in Example 4 and'40 percent of a dr-n-alkylbenzene.
  • the material had the following analysis:
  • Sulfur, weight EXAMPLE 6 This example illustrates the preparation of a dispersion of calcium carbonate in a sulfurized alkylphenol.
  • This material contained. a mixture of sulfurized mono-C and di- C alkylphenols. It contained 73.6 percent sulfurized phenols and 26.4 percent free oil. The material contained 6.1 1 weight percent sulfur-and 0.80 weight percent chlorine-The material was stripped with an inert gas to remove impurities prior to using.
  • This material was prepared by sulfonation of a complex mixture of hydrocarbons. It contained some long chain monoalkylbenzenes and some di-n-alkylbenzenes. The material had the following analysis:
  • the calcium intennediate was a methoxy ethanol solution of cal cium methoxy ethoxide-carbonate complex containing 7.42 weight percent calcium.
  • the admixture was heated over a period of 3 hours to a final temperature of 150 C. to remove solvents. During the final one hour and 10 minutes of this heating period the admixture was blown with CO gas.
  • This material was a sulfurized mixture of monononylphenol and dinonylphenols, having the following analysis:
  • Example 3 The procedure was substantially the same as shown in Example 3, except that the product was stripped with nitrogen gas at l40-160 C. for one hour.
  • the overbasing amount (firs additon) of methoxy ethanol solution of calcium was 117.5 grams. It was added over a period of 30 minutes at a temperature of 25.5 to 52 C.
  • the neutralizing amount (second addition) of methoxy ethanol solution of calcium was 133.7 grams. It was added over a period of 45 minutes at a temperature of 75.5-77.5 C.
  • the yield of product was 352.3 grams.
  • the product had the following analyses and properties:
  • EXAMPLE 8 This example illustrates the preparation of a dispersion of magnesium hydroxide in a magnesium salt of a sulfurized alkylphenol wherein the product contained 55 percent (weight) of dispersant.
  • Example 3 The procedure was substantially the same as in Example 3 except that the product was stripped with nitrogen gas at l40-160 C. for 1 hour.
  • the overbasing amount (first addition) of methoxy solution of magnesium was 72.7 grams. It was added over a period 30 minutes at a temperature of 250 to 510 C.
  • the neutralizing amount (second addition) of methoxy ethanol solution of magnesium was 93.6 grams. It was added over a period of 45 minutes at a temperature of 80-92.5 C.
  • the yield of product was 355.7 grams.
  • the product had the following analyses and properties:
  • EXAMPLE 9 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium salt of a sulfurized alkylphenol containing 50 percent (weight) of dispersant.
  • the overbasing amount (first addition) of methoxy ethanol solution of magnesium alkoxide-carbonate complex was 46.0 grams. It was added over a period of 30 minutes at a temperature of 26.5 to 55 C.
  • the neutralizing amount (second addition) of methoxy ethanol solution of magnesium alkoxidecarbonate complex was 96.6 grams. It was added over a period of 45 minutes at a temperature of 74 to 78 C.
  • the yield of product was 346.9 grams.
  • the product had the following analyses and properties:
  • alkylphenol a sulfurized alkylphenol
  • the alkylphenol is represented by the formula wherein R is a straight or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from four to 30 carbon atoms, and n is an integer, having a value of l or 2, said alkylphenol being characterized further in that the total number of carbon atoms in the alkyl group or groups is from 8 to 40,
  • step (a) adding to the admixture of step (a) an overbasing amount of a glycol'ether solution of magnesium, calcium or barium, said glycol ether being selected from the group consisting of materials represented by the formula ROCH CH OH wherein R is a C to C alkyl group and materials represented by the formula HOCH CH OCH CH OR where R is a C to C alkyl group;
  • step (b) c. while maintaining theadmixture at a temperature higher than in step (b) and in the range of about 55 to about 100 C. adding thereto a neutralizing amount of a glycol ether solution of magnesium, calcium or barium, wherein i. the cation is the same as in step (b), and ii. the glycol ether is as defined in step (b); and
  • the overbasing amount of glycol ether solution of magnesium, calcium or barium is from about 0.1 to about 5 equivalents of metal per equivalent of alkylphenol or sulfurized alkylphenol,
  • the total amount of magnesium, calcium or barium in the glycol ether solution added in the process is from about 0.4 to about 50 parts by weight
  • step (a) (iv) the amount of water in step (a) (iv) is sufficient to provide 1.0 to 2.5 moles per mole of dispersed magnesium, calcium or barium.
  • non-volatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricatingoils.
  • process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C -C, alcohols and C, to C glycol ethers.
  • glycol ether used to prepare the glycol ether solution of magnesium, calcium or barium is monomethyl ether of ethylene glycol or monoethyl ether of ethylene glycol.
  • step (a) 5. The process of claim 4 wherein the amounts of materials in step (a) are:
  • nonvolatile diluent oil is a mineral lubricating oil.
  • process solvent is a mixture of benzene and methoxy ethanol.
  • nonvolatile diluent oil is a mineral lubricating oil.
  • step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
  • step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
  • step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
  • step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
  • a process for preparing a highly basic magnesium salt or alkylphenols and sulfurized alkylphenols wherein the process comprises:
  • g n is an integer, having a value of l or 2, said alkylphenolbeing characterized further in that the total number of carbon atoms in the alkyl group or groups is from 8 to 40,
  • step (a) adding to the admixture of step (a) an overbasing amount of a glycol ether solution of magnesium, said glycol ether being represented by the formula ROCH,CH,OH
  • R is a C to C, alkyl group
  • step (b) while maintaining the admixture at a temperature higher than in step (b) and in the range of about 55 to about C. adding thereto a neutralizing amount of a glycol ether solution of magnesium wherein the glycol ether is as defined in step (b); and
  • the overbasing amount of glycol ether soltuion of magnesium is from about 0.1 to about equivalents of magnesium per equivalent of alkylphenol or sulfurized alkylphenol,
  • the total amount of magnesium in the glycol ether solution added in the process is from about 0.4 to about parts by weight
  • step (a) (iv) is suflicient to provide 1.0 to 2.5 moles per mole of dispersed magnesium, calcium or barium.
  • nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
  • process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C,-C alcohols, and C;, to C glycol ethers.
  • step (a) The process of claim 17 wherein the amounts of materials in step (a) are parts by weight about 9 to about 70 about 20 to about 90 diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
  • process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C,C, alcohols and C to C glycol ethers.
  • nonvolatile diluent oil is a mineral lubricating oil.
  • step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per parts of alkylphenol or sulfurized alkylphenol.
  • step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
  • step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00148262A 1971-05-17 1971-05-17 Preparation of highly basic alkylphenates and sulfurized alkyphenates Expired - Lifetime US3755170A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US14826271A 1971-05-17 1971-05-17

Publications (1)

Publication Number Publication Date
US3755170A true US3755170A (en) 1973-08-28

Family

ID=22525007

Family Applications (1)

Application Number Title Priority Date Filing Date
US00148262A Expired - Lifetime US3755170A (en) 1971-05-17 1971-05-17 Preparation of highly basic alkylphenates and sulfurized alkyphenates

Country Status (10)

Country Link
US (1) US3755170A (enExample)
JP (1) JPS554091B1 (enExample)
BE (1) BE827579Q (enExample)
CA (1) CA996096A (enExample)
DE (1) DE2224073A1 (enExample)
ES (1) ES401110A1 (enExample)
FR (1) FR2137520B1 (enExample)
GB (1) GB1391847A (enExample)
IT (1) IT952098B (enExample)
NL (1) NL173539C (enExample)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4212752A (en) * 1975-07-14 1980-07-15 Liquichimica Robassomero S.P.A. Improved process for the production of an additive for lubricating oils and related product
US4221673A (en) * 1977-01-28 1980-09-09 Exxon Research & Engineering Co. Metal phenates
US4295981A (en) * 1979-07-27 1981-10-20 Burnop Victor C Production of overbased magnesium detergent additives
US5292443A (en) * 1992-08-21 1994-03-08 Texaco Inc. Process for producing neutralized sulfurized alkylphenate lubricant detergent additive
US5330665A (en) * 1982-05-22 1994-07-19 Bp Chemicals (Additives) Limited Production of either an alkaline earth metal alkyl phenate or a sulphurised alkaline earth metal alkyl phenate
US6162770A (en) * 1998-01-30 2000-12-19 Chevron Chemical Company Llc Unsulfurized alkali metal-free, additive for lubricating oils
US20040235686A1 (en) * 2003-05-22 2004-11-25 Chevron Oronite Company Llc Carboxylated detergent-dispersant additive for lubricating oils
US20170211008A1 (en) * 2014-05-28 2017-07-27 The Lubrizol Corporation Alkylphenol detergents

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4256568A (en) * 1979-11-19 1981-03-17 Exxon Research & Engineering Co. Removal of phenols from phenol-containing streams
JPS5931724A (ja) * 1982-08-16 1984-02-20 Cosmo Co Ltd 塩基性アルカリ土類金属フェネートもしくはその二酸化炭素処理物の製造法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2788325A (en) * 1953-07-27 1957-04-09 Texas Co Process for preparing magnesium alkyl phenolates
US2808377A (en) * 1956-03-30 1957-10-01 Exxon Research Engineering Co Process for preparing neutralized alkyl phenol sulfides
US3336224A (en) * 1965-04-28 1967-08-15 Chevron Res High alkalinity overbased phenate
US3350310A (en) * 1965-02-08 1967-10-31 Mobil Oil Corp Preparation of overbased calcium alkylphenate sulfides
US3388063A (en) * 1966-08-10 1968-06-11 Chevron Res Magnesium overbased phenate
US3474035A (en) * 1967-03-20 1969-10-21 Texaco Inc Lubricating oil containing overbased sulfurized calcium alkylphenolate
US3493516A (en) * 1966-05-04 1970-02-03 Chevron Res Carboxylate modified phenates

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2409687A (en) * 1943-05-10 1946-10-22 Standard Oil Dev Co Sulfur and metal containing compound
US2680096A (en) * 1951-02-12 1954-06-01 California Research Corp Process for preparing sulfurized polyvalent metal phenates
BE519501A (enExample) * 1952-04-29
DE1028268B (de) * 1954-01-04 1958-04-17 Lubrizol Corp Verfahren zur Herstellung eines fluessigen, oelloeslichen Zusatzstoffes fuer Schmieroele
US3062897A (en) * 1959-11-02 1962-11-06 Fmc Corp Process for the manufacture of barium alkyl phenates
DE1188662B (de) * 1963-07-11 1965-03-11 Standard Elektrik Lorenz Ag Ausgleichsnetzwerk fuer Fernsprech-Teilnehmerstationen
GB1105217A (en) * 1965-10-05 1968-03-06 Lubrizol Corp Process for preparing basic metal phenates
US3367867A (en) * 1966-01-04 1968-02-06 Chevron Res Low-foaming overbased phenates

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2788325A (en) * 1953-07-27 1957-04-09 Texas Co Process for preparing magnesium alkyl phenolates
US2808377A (en) * 1956-03-30 1957-10-01 Exxon Research Engineering Co Process for preparing neutralized alkyl phenol sulfides
US3350310A (en) * 1965-02-08 1967-10-31 Mobil Oil Corp Preparation of overbased calcium alkylphenate sulfides
US3336224A (en) * 1965-04-28 1967-08-15 Chevron Res High alkalinity overbased phenate
US3493516A (en) * 1966-05-04 1970-02-03 Chevron Res Carboxylate modified phenates
US3388063A (en) * 1966-08-10 1968-06-11 Chevron Res Magnesium overbased phenate
US3474035A (en) * 1967-03-20 1969-10-21 Texaco Inc Lubricating oil containing overbased sulfurized calcium alkylphenolate

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4212752A (en) * 1975-07-14 1980-07-15 Liquichimica Robassomero S.P.A. Improved process for the production of an additive for lubricating oils and related product
US4221673A (en) * 1977-01-28 1980-09-09 Exxon Research & Engineering Co. Metal phenates
US4295981A (en) * 1979-07-27 1981-10-20 Burnop Victor C Production of overbased magnesium detergent additives
US5330665A (en) * 1982-05-22 1994-07-19 Bp Chemicals (Additives) Limited Production of either an alkaline earth metal alkyl phenate or a sulphurised alkaline earth metal alkyl phenate
US5292443A (en) * 1992-08-21 1994-03-08 Texaco Inc. Process for producing neutralized sulfurized alkylphenate lubricant detergent additive
US6162770A (en) * 1998-01-30 2000-12-19 Chevron Chemical Company Llc Unsulfurized alkali metal-free, additive for lubricating oils
US20040235686A1 (en) * 2003-05-22 2004-11-25 Chevron Oronite Company Llc Carboxylated detergent-dispersant additive for lubricating oils
US7163911B2 (en) 2003-05-22 2007-01-16 Chevron Oronite Company Llc Carboxylated detergent-dispersant additive for lubricating oils
US20070105730A1 (en) * 2003-05-22 2007-05-10 Chevron Oronite Company Llc Carboxylated detergent- disperant additive for lubricating oils
US20170211008A1 (en) * 2014-05-28 2017-07-27 The Lubrizol Corporation Alkylphenol detergents

Also Published As

Publication number Publication date
ES401110A1 (es) 1975-02-01
NL7206607A (enExample) 1972-11-21
FR2137520A1 (enExample) 1972-12-29
BE827579Q (fr) 1975-07-31
GB1391847A (en) 1975-04-23
JPS554091B1 (enExample) 1980-01-29
IT952098B (it) 1973-07-20
CA996096A (en) 1976-08-31
FR2137520B1 (enExample) 1976-08-06
NL173539C (nl) 1984-02-01
DE2224073A1 (de) 1972-11-30

Similar Documents

Publication Publication Date Title
US3178368A (en) Process for basic sulfurized metal phenates
US5534168A (en) Preparation of overbased magnesium sulphonates
US3493516A (en) Carboxylate modified phenates
US4057504A (en) Method of preparing overbased lubricating oil additives
DE69326815T2 (de) Zweitakt schmiermittel und verfahren zu seiner verwendung
EP0092415B1 (en) Preparation of overbased magnesium phenates
EP0450874B1 (en) Overbased calixarates, process for their production, compositions containing them and use as lubricating oil additives
EP0095322B1 (en) Process for the production of an overbased sulphurised alkaline earth metal alkyl phenate
US4973411A (en) Process for the preparation of sulfurized overbased phenate detergents
EP0425513B1 (en) Lubricant overbased phenate detergent with improved water tolerance
US3755170A (en) Preparation of highly basic alkylphenates and sulfurized alkyphenates
EP0021838B1 (en) A process for the production of oil-soluble polyol esters of dicarboxylic acid materials in the presence of a metal salt of a hydroxy aromatic compound
US3746698A (en) Preparation of highly basic,sulfurized alkylphenols
EP0312315B1 (en) Use of an overbased magnesium sulphonate composition
US5330664A (en) Neutral and low overbased alkylphenoxy sulfonate additive compositions derived from alkylphenols prepared by reacting an olefin or an alcohol with phenol in the presence of an acidic alkylation catalyst
US3336224A (en) High alkalinity overbased phenate
US5330663A (en) Neutral and low overbased alkylphenoxy sulfonate additive compositions
EP0699740B1 (en) Overbased metal salts, their preparation and use
US3718589A (en) Preparation of neutral and highly basic alkylphenates and sulfurized alkylphenates
KR950009006B1 (ko) 그리이스 및 기어 윤활유 조성물
US4614602A (en) Lubricant overbased detergent-dispersants with improved solubility
US3806454A (en) Process for preparing barium-containing dispersion
EP0462762B1 (en) Sulfite overbased products and process
US5250204A (en) Sulfite overbased products and process
US4196089A (en) Preparation of overbased magnesium sulfurized phenates