US3755173A - Alkenyl halolactone esters and acids and lubricants containing them - Google Patents

Alkenyl halolactone esters and acids and lubricants containing them Download PDF

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US3755173A
US3755173A US00169544A US3755173DA US3755173A US 3755173 A US3755173 A US 3755173A US 00169544 A US00169544 A US 00169544A US 3755173D A US3755173D A US 3755173DA US 3755173 A US3755173 A US 3755173A
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composition according
lubricating composition
alkenyl
lubricating
polyol
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B Kennedy
W Lowe
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Chevron USA Inc
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Chevron Research and Technology Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/95—Esters
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    • C10M131/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen
    • C10M131/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen, halogen and oxygen
    • C10M131/12—Acids; Salts or esters thereof
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/044—Acids; Salts or esters 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated 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
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral 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
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
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    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/02—Esters of silicic acids
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    • C10N2010/04—Groups 2 or 12
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions
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Definitions

  • an. effective ashless. detergent/dispersant additive which consists of the reaction product of (l) a monool or polyol and (2.) an alkenyl chlorolactone or bromolactone alkyl ester or acid which has been prepared by the reaction of alkenyl succinic anhydride, chlorine or bromine, and a low molecular weight alkanol or water.
  • the invention also encompasses the lubricant compositions comprising an oil of lubricating viscosity and the described additive.
  • compositions of this invention are novel metalfree (ashless) lubricating oil detergency/dispersancy additives and lubricants containing those additives. These lubricants provide excellent detergency and/or dispersancy in both diesel and gasoline internal combustion engines. Iln diesel engine tests in which the engine is operated under extremely severe conditions, these lubricants have proved to be quite efi'ective in: maintaining a low level of deposits: in the engines.
  • additive imparts to the lubricant a number of desirable properties, as illustrated in the examples below.
  • the additive composition, of this invention is the reaction product of a monool or polyol and an alkenyl chlorolactone or bromolactone alkyl ester oraci'd.
  • the ester or acid is prepared by reacting an alkenyl succinic.
  • R is an alkenyl group most conveniently obtained by polymerizing an olefin or mixture of olefins containing from about two to five carbon atoms.
  • the molecular weight of the resulting polymer will generally be in the range of about 400 to 3,000 and more usually in the range of about 700 to 1,400.
  • Useful olefins are illustrated by ethylene, propylene, l-butene, Z-butene, isobutene, l-pentene and mixtures thereof, preferably isobutene.
  • the methods of polymerizing such olefins to polymers of the designated molecular weight are well known in the art and do not require exemplification here. (See, for example, US. Pat. Nos. 3,024,195 and 3,018,250.)
  • the alkenyl succinic anhydride is converted to the alkenyl chloroor bromolactone alkyl ester or acid by reaction in solution with chlorine or bromine and, for the ester, a low molecular weight alkanol, or, for the acid,.water.
  • the low molecular weight alkanols are those containing one to three carbon atoms and no functional groups other than a single hydroxy group.
  • the alkanols thus include methanol, ethanol, 1-
  • propanol and 2-propanol.
  • methanol and ethanol (particularly methanol) are preferred.
  • the halogens which may be used to produce the alkenyl halolactone ester or acid are chlorine and bromine
  • the chlorine is usually present as chlorine gas, which is bubbled through the reaction mixture.
  • Bromine is present as liquid in the reaction mixture.
  • a compound which will donate chlorine or bromine such as N-bromosuccinimide
  • the residue of such a compound should also be readily separable from the reaction mixture.
  • alkanol or water is ordinarily carried out at ambient reaction is slightly exothermic. If desired, cooling.
  • reaction mixture may be maintained at a temperature at or slightly above ambient temperature. Following reaction the solvent and excess reactants are removed and the product recovered.
  • the alkenyl halolactone alkyl ester or acid product will generally contain about 1-8 weight percent chlorine or bromine.
  • the infrared spectrum of the product will show distinctive peaks at about l,775-l,780 cm (lactone) and about 1,740 cm (ester) or about 1,700 cm (acid).
  • the alkenyl halolactone alkyl ester or acid and the monoor polyol are reacted with heating to a temperature in the range of l70-l90 C. for a period of l-24 hours.
  • the reaction is conducted in the presence of a small amount of hydroxide anion and under a nitrogen or other inert gas atmosphere. Usually approximately equimolar amounts of reactants are used, although a small excess of monoor polyol may be used if desired.
  • the esterification or transesterification reaction may be caused to proceed to completion by removal during the reaction of the low molecular weight alkanol or water produced.
  • the product may be recovered by conventional means, including separation of unrcacted monoor polyol, which may be recovered.
  • the monools or polyols which are useful in the above-described esterification or transesterification reaction may be selected from any of the following: l) aliphatic or alicyclic monohydric and polyhydric compounds, either saturated or unsaturated, and (2)'aromatic monohydric or polyhydric compounds. Preferred are the polyhydric compounds having 'at least three hydroxyl groups. Also preferred are those monohydric or polyhydric compounds containing only carbon, hydrogen, and oxygen atoms.
  • the aliphatic or alicyclic alcohols from which the esters may be-derived preferably contain up to about 40 aliphatic carbon atoms. They may be monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, B-phenylethyl alcohol, 2- methylcyclohexanol, monomethyl ether of ethylene gylcol, monobutyl ether of ethylene glycol, monopropyl ether of diethylene glycol, monododecyl ether of triethylene glycol, monooleate of ethylene glycol, monostearate of diethylene glycol, sec.-pentyl alcohol, tert.-butyl alcohol, and dioleate of glycerol.
  • the polyhydric alcohols preferably contain from 2 to about hydroxyl groups. They are illustrated by ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols in which the alkylene group contains from two to about eight carbon atoms.
  • polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, 9,10-dihydroxy stearic acid, methyl ester of 9,10-dihydroxy stearic acid, 1,2- butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol, 1,2- cyclohexanediol, and xylene glycol.
  • Carbohydrates such as sugars, starches, celluloses, etc., likwise may yield the esters of this invention.
  • the carbohydrates may be exemplified by glucose, fructose; sucrose, rhamnose, mannose, glyceraldehyde, and galactose.
  • An expecially preferred class of polyhydric alcohols are those having at least three hydroxyl groups, such as pentaerythritol, sorbitol, mannitol, and arabitol.
  • Soluv bility of some polyhydricalcohols may be increased by esterifying soniekof the hydroxyl groups with 'a monocarboxylic acid having from about 8 to about 30 carbon atoms such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid, or tall oil acid.
  • Examples of such-partially esterified polyhydric alcohols are the monooleate of sorbitol, distearate of sorbitol, monooleate of glycerol, monostearate of glycerol, and didodecanoate of erythritol.
  • esters of this invention may also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, l-cyclohexene-3-ol, and oleyl alcohol.
  • aromatic hydroxy compounds from which the esters of this invention may be derived are illustrated by the following specific examples: phenol, B-naphthol, a-naphthol, cresol, resorcinol, catechol, p,p'- dihydroxybiphenyl, 2-chlorophenol, 2,4-dibutylphenol, propene tetramer-substituted phenol, didodecylphenol, 4,4'-methylene-bis-phenol, a-.decyl-B-naphthol, polyisobutene(molecular weight of 300-2,000)- substituted phenol, the condensation product of heptylphenol with 0.5 mole of formaldehyde, the condensation product of octylphenol with acetone, di(hydroxyphenyl)oxide, and 4-cyclohexylphenol. Phenol and alkylated phenols having up to three alkyl substituents are preferred. Each of the alkyl
  • the alkenyl halolactone monoor polyol ester reaction product will contain 0.5-5 weight percent chlorine or bromine, and its infrared spectrum will contain peaks at about 1,740 cm* (ester), 1,780 cm (lactone), and 3,450 cm (hydroxyl).
  • the lubricant compositions of this invention are prepared by blending the ester reaction product as an additive into an oil of lubricating viscosity.
  • Suitable oils are derived from either natural or synthetic sources and generally have viscosities of from about 35 to 50,000 Saybolt Universal Seconds (SUS) at 100 F.
  • natural hydrocarbonaceous oils are paraffin-base, naphthenic-base, asphaltic-base and mixed-base oils.
  • hydrocarbon oils such as polymers of various olefins, generally of from two to eight carbon atoms, and alkylated aromatic hydrocarbons
  • nonhydrocarbon oils such as polyalkylene oxide, aromatic ethers, carboxylate esters, phosphate esters and silicon esters.
  • the preferred media are the hydrocarbonaceous media, both natural and synthetic.
  • the above oils may be used individually or together whenever miscible or made so by the use of mutual solvents.
  • the detergents and/or dispersants of this invention When the detergents and/or dispersants of this invention are compounded with lubricating oils for use in an engine, they will be present in a concentration of at least about 0.01 weight percent and usually not more than 20 weight percent, more usually in the range of about 0.5-15, and preferably l-lO, weight percent. Often higher concentrations are used in diesel engine lubricants than are used in gasoline engine lubricants.
  • the compounds can also be prepared as concentrates due to their excellent compatibility with oils. As concentrates, the compounds of this invention will generally rangefrom about l0-70 weight percent, more usually.from about 20-50 weight percent of the total composition.
  • 0.l-l5 weight percent more usually from about 0.5-5 weight percent.
  • the individual additives may vary from about 0.0l-5 weight percent of the composition.
  • the product was recovered by boiling off the hexanes and stripping under vacuum.
  • 1,242g. of the chlorolactone pentaerythritol ester reaction product were recovthis invention will include (in addition to the ester reacl0 ered.
  • This product contained approximately 2.6 weight tion product detergent/dispersant) l-50 mM./kg. of a dihydrocarbyl phosphorodithioate, wherein the hydrocarbyl groups are from about four to 36 carbon atoms.
  • the hydrocarbyl groups will be alkyl or alkaryl groups.
  • l-lydrocarbyl designates an organic radical composed solely of carbon and hydrogen, and which may be aliphatic, alicyclic, or aromatic.
  • Example 1 Preparation of Alkenyl Chlorolactone Methyl Ester To a 3-liter flask equipped with a stirrer were charged l,300 g. of oil-free polyisobutyl succinic anhydride (in which the isobutyl portion of the molecule had a molecular weight of approximately 950), 100 cc. of methanol and 800 cc. of benzene solvent. These reagents were thoroughly mixed and then chlorine gas was bubbled through the mixture while stirring for 3 55 hours. During this period, the temperature of the reaction mixture ranged between 77 F. and 1 F.
  • reaction product will contain a 1 variety of compounds, the structures of which are not known with certainty. However, it is believed that among the reactions occurring are:
  • Example 3 Preparation of Alkenyl Chlorolactone Acid To a l-liter flask equipped with a stirrer and heating mantle were charged 325 g. of oil-free polyisobutenyl succinic anhydride of the type described in Example l, 13 cc. of water, and 200 cc. of benzene solvent. Chlorine gas was bubbled through the mixture for about one hour. During this hour, the temperature ranged between 78 F. and l20 F. Thereafter nitrogen gas was bubbled through the chlorinated mixture for two hours and the product was recovered by stripping under vacuum. 339 g. of product were obtained, with a chlorine content of 3.9 weight percent.
  • Example 4 Reaction of Pentaerythritol and Alkenyl Chlorolactone Acid 167 g. of the reaction product of Example 3 were mixed with 20 g. of pentaerythritol and 0.2 g. of NaOH. The reaction was conducted as in Example 2, to yield a product having a chlorine content of 2.27 weight percent. The infrared spectrum included peaks centered at about 1,730 cm", 1,780 cm, and 3,460 cm". The product had a total base number (ASTM D-664) of 76.5 (average of two runs). The typical reactions believed to be occurring are esterifications with water as a product analogous to the transesterifications illustrated in Example 2.
  • the engine is operated with a Ford economy carburetor-with a manually adjustable jet in place of the power valve. Fuel and air feed rates are measured, and the air/fuel ratio controlled to 15.0 i 0.5 by adjusting the jet during Cycle 3 running (see below).
  • the engine is run on a three-cycle test series. The conditions of each cycle are described on Table l following.
  • the lubricant compositions used were composed of a hydrocarbon lubricating oil prepared by blending a 200 neutral oil, a 350 neutral oil and a 150 bright stock, and as additives, 50 mM./kg. of an overbased calcium sulfonate, l5 mM./kg. of a zinc dialkyldithiophosphate and the indicated weight percent of the test additive.
  • PBCLPE is an abbreviation for the polyisobutenylchlorolactone pentaerythritol ester of Example 2.
  • Succinimide A refers to a commercial polyisobutenyl succinimide produced by reacting a polyisobutenyl succinic anhydride (PIBSA) with tetraethylene pentamine (TEPA).
  • PIBSA polyisobutenyl succinic anhydride
  • TEPA tetraethylene pentamine
  • the polyisobutenyl portion of the molecule has a molecular weight of approximately 950 and the mole ratio of TEPA/PIBSA is 0.87.
  • Ester A refers to a commercial ester prepared by reacting pentaerythritol with a polyisobutenyl succinic anhydride in which the polyisobutenyl portion has a molecular weight of approximately 950-1,000.
  • esters of this invention are good antivarnish additives and that lubricants containing these esters are comparable in performance to lubricants containing commercial additives in their performance in automobile gasoline engines.
  • Example 6 I BMEP Caterpillar Diesel Engine Test The purpose of this test was to illustrate the performance of the lubricants of this invention in diesel engines.
  • This test utilizes a single-cylinder Caterpillar supercharged diesel engine having a 5 A inches bore by 6 55 inches stroke. The engine is operated at 180 psi BMEP, a fuel input of 7,460 BTU/minute, an intake air pressure of 70 inches of mercury and a power output of 55 BHP. Other operating conditions are the same as those used in the well-known Caterpillar l-G test.
  • the test formulation was composed of a hydrocarbon lubricating oil prepared by blending a 250 neutral oil and a 150 bright stock, mM./kg.
  • Succinimide B refers to a commercial succinimide similar to Succinimide A" above, but prepared by reaction with triethylene tetramine (TETA) instead of TEPA; the TETA/PIBSA mole ratio is 0.5.
  • TETA triethylene tetramine
  • the test engine was run for hours, dismantied, and the piston inspected for groove and land deposits. Each groove is rated on a scale of 0-100, with 0 being a clean groove and 100 being a groove completely filled with deposits. Each land is rated on a scale of 0-800, with 0 being a clean land and 800 being a completely dirty land.
  • Example 7 Neutralization Rate Test This is a bench test designed to correlate with the well-known Sequence IlB Automobile Engine Rust Test. This test has been found to give an accurate'prediction of the performance of a given additive in the Sequence lIB test.
  • a 100 ml. solution of 0.01 N aqueous l-lCl is placed in a Beckman Expandomatic pH meter. 50 ml. of the test oil are layered into the aqueous phase and then mixed. During mixing the pH of the mixture is plotted as a function of time.
  • test results are reported as the number of minutes elapsed from the beginning of mixing until the curve of pl-l-versus-time shows a point of inflection; the more quickly this point of inflection occurs, the more rapidly the acid has been neutralized by the lubricant composition.
  • the test formulations were composed of a 100 neutral oil, 25 mM./kg. of the over-based calcium sulfonate of Example 6, 40 mMJkg. of the over-based sulfurized calcium alkyl phenate of, Example 6, l mM./kg. of the zinc dialkaryldithiophosphate of Example 6 and 8 percent of the test additive.
  • a lubricating composition comprising an oil of lubricating viscosity and from 0.01 to percent by weight of a lubricating oil additive consisting essentially of the reaction product of a monool or polyol and an alkenyl halolactone alkyl ester or acid; said ester being the reaction product of (1) an alkenyl succinic anhydride, wherein the alkenyl group has a molecular weight in the range of from 400 to 3,000, (2) a halogen selected from the group consisting of chlorine and bromine, and (3) a C -C alkanol; and said acid being the reaction-product of (I) an alkenyl succinic anhydride, wherein the alkenyl group has a molecular weight in the range of from 400 to 3,000, (2) a halogen selected from the group consisting of chlorine and bromine, and (3) water.
  • a lubricating oil additive consisting essentially of the reaction product of a monool or polyol and an alkeny
  • a lubricating composition according to claim 1 containing from 0.01 to 20 percent by weight of said lubricating oil additive. i V v p 3. A lubricating composition according to, claim l containing from i to IO'percent by weight of saidlubricating oil additive.

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  • Polyesters Or Polycarbonates (AREA)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3936472A (en) * 1973-01-19 1976-02-03 Mobil Oil Corporation Lactone acid synthesis
US3997569A (en) * 1972-11-08 1976-12-14 Texaco Inc. Method for preparing a lactone reaction product
US4047899A (en) * 1974-02-28 1977-09-13 Texaco Inc. Method for preparing a lactone reaction product
DE2757767A1 (de) * 1977-02-14 1978-10-19 Exxon Research Engineering Co Laktonester, verfahren zu ihrer herstellung und ihre verwendung als additive
US4239633A (en) * 1979-06-04 1980-12-16 Exxon Research & Engineering Co. Molybdenum complexes of ashless polyol ester dispersants as friction-reducing antiwear additives for lubricating oils

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4062786A (en) * 1976-09-24 1977-12-13 Exxon Research And Engineering Company Lactone oxazolines as oleaginous additives

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3331776A (en) * 1962-10-04 1967-07-18 Shell Oil Co Lubricating oil composition
US3509052A (en) * 1968-09-13 1970-04-28 Lubrizol Corp Lubricating compositions
US3522179A (en) * 1963-04-23 1970-07-28 Lubrizol Corp Lubricating composition containing esters of hydrocarbon-substituted succinic acid
US3620977A (en) * 1968-12-17 1971-11-16 Chevron Res Reaction product of alkylene polyamines and chlorinated alkenyl succinic acid derivatives

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3331776A (en) * 1962-10-04 1967-07-18 Shell Oil Co Lubricating oil composition
US3522179A (en) * 1963-04-23 1970-07-28 Lubrizol Corp Lubricating composition containing esters of hydrocarbon-substituted succinic acid
US3509052A (en) * 1968-09-13 1970-04-28 Lubrizol Corp Lubricating compositions
US3620977A (en) * 1968-12-17 1971-11-16 Chevron Res Reaction product of alkylene polyamines and chlorinated alkenyl succinic acid derivatives

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3997569A (en) * 1972-11-08 1976-12-14 Texaco Inc. Method for preparing a lactone reaction product
US3936472A (en) * 1973-01-19 1976-02-03 Mobil Oil Corporation Lactone acid synthesis
US4047899A (en) * 1974-02-28 1977-09-13 Texaco Inc. Method for preparing a lactone reaction product
DE2757767A1 (de) * 1977-02-14 1978-10-19 Exxon Research Engineering Co Laktonester, verfahren zu ihrer herstellung und ihre verwendung als additive
US4239633A (en) * 1979-06-04 1980-12-16 Exxon Research & Engineering Co. Molybdenum complexes of ashless polyol ester dispersants as friction-reducing antiwear additives for lubricating oils

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NL7210737A (enrdf_load_stackoverflow) 1973-02-07
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FR2148080B1 (enrdf_load_stackoverflow) 1976-08-13
CA990731A (en) 1976-06-08
FR2148080A1 (enrdf_load_stackoverflow) 1973-03-11

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