US3718589A - Preparation of neutral and highly basic alkylphenates and sulfurized alkylphenates - Google Patents

Preparation of neutral and highly basic alkylphenates and sulfurized alkylphenates Download PDF

Info

Publication number
US3718589A
US3718589A US00176676A US3718589DA US3718589A US 3718589 A US3718589 A US 3718589A US 00176676 A US00176676 A US 00176676A US 3718589D A US3718589D A US 3718589DA US 3718589 A US3718589 A US 3718589A
Authority
US
United States
Prior art keywords
alkylphenol
process defined
parts
sulfurized
weight
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
US00176676A
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 US3718589A publication Critical patent/US3718589A/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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
    • C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • 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
    • C10M2219/04—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 A process for preparing neutral and highly basic magnesium alkylphenates or sulfurized alkylphenates wherein the process comprises:
  • alkaline earth metal alkylphenates and sulfurized alkylphenates as lubricating oil additives has long been known.
  • the presence of these materials in the lubricating oils improves the detergency characteristics, reduces engine wear, minimizes the formation of harmful deposits on engine parts, and improves the resistance of the oil to oxidation.
  • the described phenate salts can be advantageously overbased by the dispersion in the neutral phenate compositions of basic alkaline earth metal compounds.
  • the highly basic compositions as thus formulated function effectively in neutralizing harmful acidic compounds formed during the combustion of fuels used in association with the lubricating oils to which the compositions are added.
  • US. Pat. No. 2,788,325 discloses the preparation of neutral magnesium phenates by the reaction under substantially anhydrous conditions of magnesium alkoxy alkoxides with an alkylphenol, with the alkoxides being used in substantially less than the stoichiometric amount required for neutralization of the alkylphenol.
  • the water employed in admixture with the alkylphenol to be neutralized is from about 1 to about 2.5 moles of water per mole of dispersed basic alkaline earth metal compound which is to be incorporated in the product.
  • an additional amount of magnesium alcoholate which is stoichiometrically required for neutralization of the phenol is added to the reaction mixture. This addition is carried out at a relatively higher temperature than that employed during the initial addition of magnesium alcoholate.
  • the volatile materials are removed from the reaction mixture by heating.
  • the present invention concerns a process for preparing highly basic magnesium alkylphenates or sulfurized alkylphenates, wherein the process comprises the steps of:
  • step (c) The process of the present invention also contemplates the overbasing of the described neutral phenate compositions by following the neutralization step [step (c) described above] with the gradual concurrent addition to the neutral phenate compositions of an overbasing amount of carbonated magnesium alcoholate and water in a ratio of from about 1.1 to about 4 moles of water per mole of the carbonated magnesium alcoholate. This addition is carried out at a temperature of from about 55C to about 90C. After this addition is completed, volatile solvents are removed as described in step (d) above.
  • An object of the present invention is to provide an improved process by which neutral and overbased magnesium phenate compositions useful as lubricating oil additives may be prepared.
  • Another object of the invention is to provide a process for producing neutral and overbased magnesium phenate compositions having low viscosity facilitating ease of blending in lubricating oil formulations.
  • 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 eight and a maximum value of 40. Thus, when n is l, the minimum number of carbon atoms in R is eight.
  • hydrocarbon radicals examples include alkyl radicals such as butyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, 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:
  • the sulfurized alkylphenols which are useful in our process suitably contain from about 2 to about 14 percent by weight sulfur. Preferably, the amount of sulfur is from about 4 to about 12 percent by weight. It may be here pointed out that in the preparation of overbased dispersions (as contrasted with neutral dispersions), the utilization of the sulfurized alkylphenols is preferred to use of the unsulfurized alkylphenols.
  • 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 160C.
  • nonvolatile diluent oils examples include mineral lubricating oils obtained by conventional refining procedures, synthetic lubricating oils such as polymers of propylene, polyoxyalkalenes, polyoxypropylene; dicarboxylic acid esters, and esters of acids of phosphorus, synthetic hydrocarbon lubricating oils, such as di-n-alkylbenzenes and oligomers of C C a-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.
  • the process solvents which are useful in the process of the present invention have a boiling point below about l50C.
  • suitable volatile process solvents include aromatic hydrocarbons, such as benzene, toluene and xylene; aliphatic hydrocarbons, such as hexane and heptane; petroleum naphtha, glycol ethers, as hereinafter defined, and primary aliphatic C -C alcohols.
  • the carbonated magnesium alcoholates used in the process of the invention are derived from monoethers of ethylene glycol and diethylene glycol containing up to 8 carbon atoms.
  • the monoethers of ethylene glycol are also known as alkoxy alkanols, and the carbonated magnesium alcoholate complexes thereof are sometimes referred to as magnesium alkoxide-carbonate complexes.
  • the carbonated magnesium alcoholates derived from the monoethers of ethylene glycol have the generic formula:
  • Mtg- O OHQCHzOR where R is either a C to C alkyl group or an organic radical of the formula If H where R is a C to C alkyl group, and x is from 0.5 to 1.5, preferably 0.75 to 1.0.
  • the carbonated magnesium alcoholates are derived from the monoethyl and monomethyl ethers of ethylene glycol. These latter materials are available commercially under the trademarks Cellosolve and methyl Cellosolve, respectively.
  • the complexes employed contain from about 0.5 mole to about 2.0 mole of CO per mole of metal alcoholate, and preferably from about 0.8 mole to about 1.2 mole per mole of the alcoholate.
  • the magnesium content of the preferred complexes ranges from 3 weight percent to about 10 weight percent.
  • the carbonated magnesium alcoholates are added to the mixture containing the phenol compounds to be neutralized in the form of a solution of the alcoholate in glycol ether. Solutions containing from about 30 weight percent to about weight percent of the alcoholate are preferably utilized.
  • the water required during the hydrolysis of the overbasing step of the process can be water per se or an azeotrope mixture of water and glycol ether.
  • the product is improved by the addition of small amounts of oil-soluble sulfonic acid to the starting material.
  • the amount of sulfonic acid employed in such cases is from about 0.1 to about 50 parts per parts of the alkylphenol or sulfurized alkylphenol starting material.
  • the acid is preferably used in a hexane solution.
  • Particularly suitable oil-soluble sulfonic acids are those prepared from various synthetic hydrocarbon sulfonation feedstocks. These materials are usually monoor di-alkylbenzenes and generally have molecular weights of from about 300 to about 1,000. The nature and derivation of the suitable sulfonic acids are further detailed in Nield U.S. Pat. No. 3,525,599 which is incorporated herein by reference.
  • NEUTRAL PHENATE COMPOSITIONS Suitable Preferred Alkylphenol or Sulfurized Alkylphenol 5-l00 10-70 Volatile Process Solvent 5-l20 l-l00 Nonvolatile Diluent Oil 2-100 10-90 Water 0.00-1.13 0.00-0.05 Magnesium Alkoxide- Carbonate Complex 2-160 4-100 OVERBASED PHENATE COMPOSITIONS Alkylphenol (or sulfurized) 5-100 -60 Volatile Process Solvent 5-120 10-100 Nonvolatile Diluent Oil 2-100 -90 Water 0.l-l0 0.2-7.5
  • an admixture is initially fonned which contains the alkylphenol or sulfurized alkylphenol to be neutralized, nonvolatile diluent oil and a volatile process solvent. Moreover, the admixture may contain a small amount of water which is less than 1 mole of water per mole of the magnesium alkoxide-carbonate complex utilized.
  • alkylphenols which may be used in the process of the present invention as hereinbefore described, we prefer to utilize mixtures of monoalkyl and dialkylphenols, either sulfurized or unsulfurized, since we have observed that the neutral phenates yielded therefrom exhibit lower viscosity and improved oil solubility with respect to the phenates derived from the monoalkylphenol starting material.
  • the mixture contains at least 20 weight percent dialkylphenol.
  • the admixture is stirred and heated to a temperature of from about C to about 60C.
  • the temperature of the admixture is brought within the range of 50C to 60C. While the admixture is at this temperature, the stoichiometric amount of magnesium alkoxide-carbonate complex is added thereto in a gradual manner.
  • the time period over which the complex is added is not critical, it is desirable that the addition be carried out in a time period of from about 5 minutes to about 120 minutes. Preferably, the addition is carried out in a period of between about 20 minutes and about 60 minutes.
  • the addition of the complex is made in such a way that the complex is introduced to the admixture beneath the surface thereof, since generally better results are obtained.
  • the amount of the complex added is, as has been previously explained, an amount which is stoichiometrically sufficient to neutralize the alkylphenol or sulfurized alkylphenol present in the admixture.
  • the use of a stoichiometric quantity of the complex is to be contrasted with the procedure described in U. S. Pat. No. 2,788,325, and is believed to be made possible in the process of the present invention as a result of the enhanced reactivity of the carbonated alcoholate as contrasted with the noncarbonated alcoholate.
  • reaction mixture Upon completion of the addition of the complex, the reaction mixture is heated to reflux temperature, which is generally between about C to about C, and is maintained at this temperature for a period of from about 20 minutes to about 1% hours with concurrent stirring. This step is important to the procurement of complete reactivity of the stoichiometric amount of the magnesium alkoxide-carbonate complex with the alkylphenol.
  • an overbasing amount of magnesium alkoxide-carbonate complex is introduced at this point in the process, along with water or a wateralcohol azeotrope.
  • the amount of the magnesium alkoxide-carbonate complex used for the purpose is varied according to the specific complex used and to the extent of overbasing desired, but in general is from about 15 weight percent to about 40 weight percent based on the total weight of the admixture to which it .is added.
  • An amount of water is added concurrently with the complex in an amount which is a stoichiometric excess of that required to hydrolyze the complex to the alkoxy alcohol and magnesium carbonate.
  • the volatile components of the mixture are removed by distillation.
  • the distillation is continued until a bottoms temperature reaches about C to about 160C, and preferably about C. It should be here pointed out that nonvolatile diluent oil may be added to the reaction mixture at any time prior to this point in the process, provided the total amount present does not exceed the 100 weight parts previously referred to.
  • this temperature is maintained and the reaction mixture is then subjected to stripping of residual volatile materials therefrom by bubbling an inert gas, and preferably, carbon dioxide, through the mixture for a period of from about 30 minutes to 1% hours.
  • an inert gas and preferably, carbon dioxide
  • an additional amount of a nonvolatile diluent oil can be added to the product at this time.
  • EXAMPLE 1 This example illustrates the preparation of a neutral magnesium alkylphenate solution using the process of the present invention.
  • This alkylphenol contained about 97 weight percent mono-p-nonylphenol having a molecular weight of 220.3 and containing 3 weight percent free oil.
  • the nonyl side chain was branched.
  • This oil was a commercially available, nonvolatile naphthenic oil. ""This material contained 7.9 weight percent magnesium and 14.3 weight percent carbon dioxide.
  • EXAMPLE 2 This example illustrates the preparation of a neutral magnesium alkylphenate composition utilizing an uncarbonated magnesium alcoholate for neutralization.
  • Example 2 the same alkylphenol was employed as that which was used in Example 1, and this material was mixed with the same nonvolatile naphthenic oil used in Example 1 in amounts equivalent to those there used.
  • the admixture also contained 100 grams of nhexane.
  • To the admixture as thus constituted were added 68.5 grams of magnesium ethoxy ethoxide (magnesium methyl Cellosolve) which contained 9.2 weight percent magnesium and 0.4 weight percent carbon dioxide.
  • the addition was carried out as described in Example 1, and was followed by heating the mixture to reflux temperature and retaining it at this temperature for a period of 1 hour with concurrent stirring. After this, the volatile materials were removed from the mixture by elevating the temperature to 150C. The mixture was then stripped with nitrogen gas for a period of 1 hour at about 150C.
  • EXAMPLE 3 This example describes two runs carried out for comparative purposes, utilizing in each case, a commercially available alkylphenol composition which contained 7 weight percent free oil, with the balance being active alkylphenols.
  • the alkylphenols in the composition comprised 65 weight percent mono-p-nonylphenol and 35 weight percent dinonylphenol.
  • the average molecular weight of the phenol materials in the composition was 250.
  • 123.5 grams of the alkylphenol composition was employed in admixture with 171.4 grams of nonvolatile naphthenic oil and 100 grams of n-hexane.
  • One of the runs was carried out using a magnesium alkoxide-carbonate complex which contained 7.9 weight percent magnesium and 14.3 weight percent carbon dioxide.
  • EXAMPLE4 A commercially available alkylphenol composition which contained weight percent mono-pdodecylphenol having a molecular weight of 262.4 and 5 weight percent of free oil was subjected to two neutralization runs in one of which, the carbonated magnesium methoxy ethoxide complexv described in Example 1 was used for neutralization, and in the other of which an uncarbonated magnesium methoxy ethoxide of the type described in Example 2 was utilized for neutralization. 121.2 grams of the alkylphenol composition was employed in admixture of 173.9 grams of nonvolatile naphthenic oil and 100 grams of hexane in each of the runs.
  • EXAMPLE 5 Two runs were carried out utilizing the procedure described in the preceding examples and each employing 143.7 grams of a commercially available alkylphenol composition which contained 3 weight percent free oil, 27 weight percent di-nonylphenol and 70 weight percent mono-p-nonylphenol. In one of the described runs, the alkylphenol composition described was mixed with 100 grams of hexane and 143.8 grams of 150 SSU naphthenic oil. In the other run, the alkylphenol composition was admixed with 100 grams of hexane and 147.6 grams of 150 SSU naphthenic oil.
  • EXAMPLE 6 This example illustrates the preparation of magnesium alkylphenate compositions derived from sulfurized phenols. Two comparative runs were carried out utilizing, in each case, a commercially available, sulfurized alkylphenol composition which contained about 48.5
  • EXAMPLE 7 This example illustrates the employment of the present invention in the production of an overbased magnesium alkylphenate dispersion, using a small amount of an oil-soluble sulfonic acid in the starting material.
  • the hexane solution contained 29 weight percent of a sulfonic acid composition derived from alkylbenzenes and having a combining weight of 488.
  • the sulfonic acid acidity of the solution was 0.587 meqjgli, and the acid contained 10.5 weight percent nonvolatile miner 01.
  • EXAMPLE 8 an overbased composition was prepared by the process of the present invention, using a sulfurized alkylphenol starting material admixed with a minor amount of an oil soluble sulfonic acid.
  • the hexane solution contained 26.3 weight percent of a sulfonic acid composition derived from alkylbenzenes and having a combining weight of 440.
  • the sulfonic acid acidity of the solution was 0.59 meq./ g., and the acid contained 17.5 weight percent nonvolatile mineral oil.
  • the volatile solvents were then removed by distillation to a bottoms temperature of 150C.
  • the product was stripped by bubbling CO, therethrough for a period of 1 hour while maintaining the temperature between 140C and 160C.
  • the final product had a base number of 248, and a viscosity at 210F of 248 centistokes.
  • a process for preparing a magnesium phenatecontaining composition comprising:
  • alkylphenol i. about 5 to about parts by weight of alkylphenol or sulfurized alkylphenol, wherein 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 1 or 2, said alkylphenol being characterized further in that the total number of alkyl group carbon atoms is from eight to 40;
  • magnesium alcoholate contains from about 0.5 mole to about 2.0 moles of CO, per mole of metal alcoholate;
  • alkylphenol employed is a mixture containing at least 20 weight percent dialkylphenol with the balance being a monoalkylphenol.
  • nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
  • 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) 6. The process defined in claim 1 wherein the amounts of materials admixed in step (a) are:
  • magnesium alcoholate is derived from the monomethyl ether of ethylene glycol or the monoethyl ether of ethylene glycol, and contains from about 0.8 mole to about 1.2 mole of C0 per mole of magnesium alcoholate.
  • alkylphenol employed is a mixture containing at least 20 weight percent dialkylphenol with the balance being a monoalkylphenol.
  • nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
  • step (a) The process defined in claim 12 wherein the amounts of materials admixed in step (a) are:
  • step (a) 19. The process defined in claim 14 wherein the amounts of materials admixed in step (a) are:
  • 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.
  • nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
  • step (a) contains additionally from about 0.1 to about 50 parts of an oil-soluble sulfonic acid per l00 parts of alkylphenol or sulfurized alkylphenol.
  • step (a) contains additionally from about 0.1 to about 50 parts of an oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00176676A 1971-08-31 1971-08-31 Preparation of neutral and highly basic alkylphenates and sulfurized alkylphenates Expired - Lifetime US3718589A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US17667671A 1971-08-31 1971-08-31

Publications (1)

Publication Number Publication Date
US3718589A true US3718589A (en) 1973-02-27

Family

ID=22645374

Family Applications (1)

Application Number Title Priority Date Filing Date
US00176676A Expired - Lifetime US3718589A (en) 1971-08-31 1971-08-31 Preparation of neutral and highly basic alkylphenates and sulfurized alkylphenates

Country Status (8)

Country Link
US (1) US3718589A (enExample)
JP (1) JPS5938212B2 (enExample)
BE (1) BE827090Q (enExample)
CA (1) CA992104A (enExample)
DE (1) DE2236189C2 (enExample)
FR (1) FR2150718B1 (enExample)
GB (1) GB1392255A (enExample)
IT (1) IT961841B (enExample)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2429203A1 (fr) * 1978-06-20 1980-01-18 Witco Chemical Corp Procede de preparation de phenates sulfures de magnesium surbasiques
US4295981A (en) * 1979-07-27 1981-10-20 Burnop Victor C Production of overbased magnesium detergent additives
WO1987003868A1 (en) * 1985-12-20 1987-07-02 The Lubrizol Corporation Basic metal salts having improved color and stability and vinyl halide polymers containing same
US5854184A (en) * 1996-04-25 1998-12-29 Institut Francais Du Petrole Colloidal products, their preparation and their uses
US20190177636A1 (en) * 2014-05-28 2019-06-13 The Lubrizol Corporation Alkylphenol detergents

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6337516U (enExample) * 1986-08-25 1988-03-10
GB8730220D0 (en) * 1987-12-29 1988-02-03 Exxon Chemical Patents Inc Detergents
JPH068201U (ja) * 1992-07-02 1994-02-01 株式会社四国製作所 穀粒選別機の選別済穀粒袋詰め装置

Citations (3)

* 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
US2895913A (en) * 1957-05-28 1959-07-21 Continental Oil Co Magnesium containing organic compositions and method of preparing the same
US2916454A (en) * 1957-02-18 1959-12-08 Socony Mobil Oil Co Inc Preparation of complex carbonated metal salts of alkyl phenol sulfides and mineral oil fractions containing the same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US26811A (en) * 1860-01-10 Seth boyden
US3036971A (en) * 1958-12-24 1962-05-29 Socony Mobil Oil Co Inc Lubricating oils containing carbonated basic sulfurized calcium phenates
NL262166A (enExample) * 1960-03-16
US3336224A (en) * 1965-04-28 1967-08-15 Chevron Res High alkalinity overbased phenate
USRE26811E (en) * 1965-08-23 1970-03-03 Basic, sulfurized phenates and salicylates and method for their preparation
NL134001C (enExample) * 1965-10-29
US3367867A (en) * 1966-01-04 1968-02-06 Chevron Res Low-foaming overbased phenates
GB1132040A (en) * 1966-03-31 1968-10-30 Monsanto Co Complex salts of alkyl phenols and alkyl phenol sulphides

Patent Citations (3)

* 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
US2916454A (en) * 1957-02-18 1959-12-08 Socony Mobil Oil Co Inc Preparation of complex carbonated metal salts of alkyl phenol sulfides and mineral oil fractions containing the same
US2895913A (en) * 1957-05-28 1959-07-21 Continental Oil Co Magnesium containing organic compositions and method of preparing the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2429203A1 (fr) * 1978-06-20 1980-01-18 Witco Chemical Corp Procede de preparation de phenates sulfures de magnesium surbasiques
US4196089A (en) * 1978-06-20 1980-04-01 Witco Chemical Corporation Preparation of overbased magnesium sulfurized phenates
US4295981A (en) * 1979-07-27 1981-10-20 Burnop Victor C Production of overbased magnesium detergent additives
WO1987003868A1 (en) * 1985-12-20 1987-07-02 The Lubrizol Corporation Basic metal salts having improved color and stability and vinyl halide polymers containing same
US5854184A (en) * 1996-04-25 1998-12-29 Institut Francais Du Petrole Colloidal products, their preparation and their uses
US20190177636A1 (en) * 2014-05-28 2019-06-13 The Lubrizol Corporation Alkylphenol detergents
US11466226B2 (en) * 2014-05-28 2022-10-11 The Lubrizol Corporation Alkylphenol detergents

Also Published As

Publication number Publication date
DE2236189C2 (de) 1983-12-15
CA992104A (en) 1976-06-29
DE2236189A1 (de) 1973-03-01
GB1392255A (en) 1975-04-30
IT961841B (it) 1973-12-10
FR2150718B1 (enExample) 1976-08-13
JPS4834863A (enExample) 1973-05-22
JPS5938212B2 (ja) 1984-09-14
FR2150718A1 (enExample) 1973-04-13
BE827090Q (fr) 1975-07-16

Similar Documents

Publication Publication Date Title
US3493516A (en) Carboxylate modified phenates
US3178368A (en) Process for basic sulfurized metal phenates
EP0273588B2 (en) Sulphurised alkaline earth metal hydrocarbyl phenates, their production and use thereof
EP0347103B1 (en) A process for the production of a lubricating oil additive concentrate
JP2763887B2 (ja) 塩基性塩の製造方法、製造された塩およびこの種の塩を含有する油組成物
US3150088A (en) Highly basic calcium-containing additive agent
US3632600A (en) Derivatives of aliphatic-hydrocarbyl substituted heterocyclic nitrogen compounds
US3150089A (en) Highly basic magnesium containing additive agent
US4171269A (en) Sulfurized lubricant composition
EP0450874B1 (en) Overbased calixarates, process for their production, compositions containing them and use as lubricating oil additives
DE69326815T2 (de) Zweitakt schmiermittel und verfahren zu seiner verwendung
US5330665A (en) Production of either an alkaline earth metal alkyl phenate or a sulphurised alkaline earth metal alkyl phenate
US4251379A (en) Detergent-dispersants of high alkalinity for lubricating oils and process for their preparation
US5281345A (en) Process for the preparation of a lubricating oil additive concentrate with an organic halide catalyst
US3718589A (en) Preparation of neutral and highly basic alkylphenates and sulfurized alkylphenates
US4629578A (en) Succinimide complexes of borated alkyl catechols and lubricating oil compositions containing same
US4169799A (en) Lubricating oil composition
US5205946A (en) Process for the production of overbased calixarates
US3755170A (en) Preparation of highly basic alkylphenates and sulfurized alkyphenates
EP0168880B1 (en) Process for the preparation of sulphurized overbased salicylates
EP0013808B1 (en) A process for the production of basic magnesium sulphonates and the products obtained by this process
US6174844B1 (en) Overbased metal calixarates, their preparation and lubricating oil compositions containing them
US3336224A (en) High alkalinity overbased phenate
US3746698A (en) Preparation of highly basic,sulfurized alkylphenols
KR950009006B1 (ko) 그리이스 및 기어 윤활유 조성물