WO2003002697A1 - Lubrifiant comprenant une base dispersible dans l'eau - Google Patents

Lubrifiant comprenant une base dispersible dans l'eau Download PDF

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Publication number
WO2003002697A1
WO2003002697A1 PCT/US2002/020394 US0220394W WO03002697A1 WO 2003002697 A1 WO2003002697 A1 WO 2003002697A1 US 0220394 W US0220394 W US 0220394W WO 03002697 A1 WO03002697 A1 WO 03002697A1
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WO
WIPO (PCT)
Prior art keywords
base
oil
lubricant
water
magnesium
Prior art date
Application number
PCT/US2002/020394
Other languages
English (en)
Inventor
Alexandra Mayhew
Stephen J. Cook
Helena M. Cressey
Ewa A. Bardasz
Original Assignee
The Lubrizol Corporation
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 The Lubrizol Corporation filed Critical The Lubrizol Corporation
Priority to JP2003509060A priority Critical patent/JP2004531638A/ja
Priority to US10/482,529 priority patent/US20040248747A1/en
Priority to CA002451220A priority patent/CA2451220A1/fr
Priority to EP02747990A priority patent/EP1404786A1/fr
Publication of WO2003002697A1 publication Critical patent/WO2003002697A1/fr

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    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
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    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C10N2050/013—Water-in-oil
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • 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

Definitions

  • Lubricants with excess basicity characterized as total . base number (TBN) are used as lubricants in internal combustion engines where atoms such as sulfur, nitrogen and carbon generate acidic combustion products that cause additional wear.
  • TBN base number
  • overbased components where bases were reacted in the oil phase with gases like CO 2 contributed basicity.
  • Water soluble or water dispersible bases can offer more neutralization capacity on a weight basis. The bases can be incorporated into an emulsified water phase.
  • lubricant One reason for having a total base number above zero in a lubricant is that acidic products are more likely to cause corrosion and wear to metal parts of a device than bases, which tend not to be involved in corrosion. Thus lubricants are formulated with sufficient excess base that over their intended lifetime, they remain neutral or slightly basic.
  • a lubricant with a high total base number is in marine diesel applications which economically burn residual fuels with a sulfur content up to about 4.5 weight percent. Due to the high amount of sulfur containing species in the economical residual fuel, the combustion products include high amount of acidic SO x which causes additional wear to the cylinder wall and the rings of the piston.
  • a solution to this lubrication/corrosion problem caused by the SO x is to include excess base in the lubricant oil so that the SO x is converted to a metal salt of the acid, which has less tendency to cause corrosion or wear.
  • the cylinder oil is injected near the rings of the piston on a continual basis to provide both continued lubrication and replace the base lost to neutralization. In these applications the cylinder lubricant is continuously consumed rather than returned to a sump.
  • the marine diesel lubricant also needs good dispersancy, oxidative stability and antiwear properties.
  • GB 789,920 describes stable dispersions of inorganic metal compounds in lubricating oil and methods of making the same.
  • Such compositions possessing increased detergency and increase reserve basicity find utility as additives in lubricating oils and possibly as corrosion inhibitors.
  • the oils soluble surface active agents are typically sulfonates and the compositions include an aliphatic alcohol having less than six carbon atoms, which is removed. It appears that a mutual solvent for the alcohol and the lubricating oil, such as benzene, is used to form a homogeneous mass that later separate into phases when the benzene and alcohol are removed.
  • Emulsions of water in oil have been described for use in hydraulic applications such as in US Patents 3,269,946; 3,281,356; 3,311,561; and 3,378,494 where fire resistance was provided by the high water content of the fluid and the use temperature was low enough that the water of the water in oil emulsion was not readily evaporated.
  • Water in oil emulsions were generally not desired in engine oils as discussed in column 1 of US Patent 3,509,052, lines 41-55, where a mayonnaiselike sludge was observed in the rocker arm covers and oil fill caps of smaller car engines when moisture condensed from the air and was emulsified into the engine oil.
  • Water in oil emulsions are also used as liquid fuels in some patent applications such as US 4,002,435.
  • a water in oil emulsion is described therein comprising a hydrocarbon, water, a water-soluble alcohol, and a novel combination of surface-active agents to provide a clear fuel, which is stable against phase separation.
  • a lubricant having a total base number above 1 mg KOH/g is described.
  • the lubricant comprises a continuous oil phase, a discontinuous water phase (or oil insoluble solvent rich phase), and a base either dissolved or dispersed in the water (or oil insoluble solvent) phase.
  • the water or oil insoluble solvent can be partially or fully removed in the final product.
  • the base in the dispersed (discontinuous) phase comprises at least a portion or all of the base in the lubricating composition.
  • Preferred bases include but are not limited to calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, potassium hydroxide, guanidine carbonate and sodium hydroxide.
  • the bases described herein can be added by simple dissolution in a solvent and are not made by prior art methods of chemically reacting at least two components within the oil phase (in situ). In marine diesel applications the total base number is desirably above 10 20, or 30 mg KOH/g.
  • the lubricant can also comprise various conventional lubricating additives to assist in the performance of the lubricant such as dispersants, detergents (including neutral and overbased detergents), extreme pressure agents, antioxidants, viscosity index modifiers, etc.
  • the lubricating oil can be selected from a wide variety of oils of API Groups I through N including mineral oils or combinations of grades or synthetic or combinations with synthetics.
  • a preferred use of the lubricant is as a cylinder lubricant in a marine diesel engine which can burn high sulfur content fuels. The high total base number of the lubricant can minimize the corrosive effect of sulfuric acid on the metal parts of the marine diesel engine.
  • the lubricant can be used in a variety of other applications, such as an internal combustion engine using low sulfur fuel, where an oil with some basicity is beneficial to avoid the effects of acidic reaction products or to extend the useful life of the lubricant.
  • Figure 1 is a plot of the total base number of the drain oils in a marine diesel engine as a function of time for the three different cylinders in the same engine.
  • Figure 2 is a plot of the total acid number of the drain oils.
  • Figure 3 is a plot of the Fe content as a function of time.
  • Figure 4 is an illustration of the equipment for the hot-bar and high temperature neutralization test for oils.
  • Lubricating oils having increased basicity due to a dispersed base therein are described.
  • the base is typically added as dissolved or dispersed base in water or other oil insoluble solvent.
  • the water or other oil insoluble solvent is then dispersed as a water or solvent in oil emulsion using the lubricating oil as the continuous phase.
  • the water or oil insoluble solvent can remain or can be partially or fully removed.
  • An emulsifier(s) is used to colloidally stabilize the dispersions.
  • a major component to the lubricating oil is a base oil, hydrocarbon in most situations although some synthetic oils that would not be strictly defined as hydrocarbon could be used (e.g. esters and polyol esters).
  • the word major is used because the amount of hydrocarbon based oil is often more than 50 weight or volume percent but it need only be the continuous phase and can be as little as 20 or 30 weight percent of the final formulation, depending on the application. In marine diesel application the hydrocarbon oil is typically more than 50 weight percent of the composition and often more than 75 weight percent of the composition.
  • Emulsifiers help emulsify the oil insoluble solvent e.g. water in the hydrocarbon oil.
  • the emulsifier(s) can be any known emulsifier useful to disperse oil insoluble solvents e.g. water in oil.
  • the emulsifiers include one high HLB (hydrophilic/lipophilic balance) emulsifier and/or one low HLB emulsifier.
  • the low HLB emulsifier can be an ester/salt made by reacting polyisobutenyl succinic anhydride with ethylene glycol and dimethyl ethanol amine in an equivalent ratio of about 2:1:2. This emulsifier can have a high molecular weight polyisobutylene chain (-1500MW).
  • the high HLB emulsifier can be an ester/salt made by reacting hexadecyl succinic anhydride with dimethylethanolamine in an equivalent ratio of about 1:1. It has a low molecular weight.
  • the emulsifier(s) can be present in any amount to effectively emulsify the water and water soluble or water dispersible base in the hydrocarbon oil phase. Preferred amounts of emulsifier include from about 0.5 to about 15 weight percent based on the weight of the formulated lubricant.
  • Oil Insoluble Solvent Water or another oil insoluble solvent or a blend(s) thereof is a necessary component to the system. Water soluble organic materials or salts can be added to depress the freezing point of the water/solvent and/or to make the water/solvent more effective in dissolving or dispersing the base. While very pure water was used in some to the examples and is preferred since it would eliminate contaminants that might interfere with other additives or function, it is anticipated that water with various impurities could be used in marine diesel applications without any significant disadvantages. Therefore water will include deionized water, tap water, recycled water, grey ship water, sea water, etc. Water can be up to 50 weight percent of the formulated lubricant as long as it remains a dispersed phase rather than the continuous phase.
  • Preferred amounts of water for marine diesel applications are from about 5 to about 50 weight percent of the formulated lubricant and more desirably from about 5 to about 30 weight percent.
  • Preferred amounts of water and/or oil insoluble solvents for lubricants for general internal combustion engines are from about 1, 2, or 3 to about 10, 20 or 30 weight percent of the formulated lubricant.
  • Oil insoluble solvents include C1-C5 monohydric and polyhydric alcohols,
  • a water soluble or water dispersible base is a necessary component to the formulated lubricant.
  • the base need not be a pure component but might be a mixture of several different bases or a partially neutralized base.
  • One part of the base might be water soluble and the other part water dispersible. It is desirable that the base has minimal particulate material after dispersion having a dimension between ten micron and a millimeter, these may be present in small amounts and can be filtered out if they become a problem (either before or after emulsifying the particulate material) such a settling or become involved plugging lines or orifices.
  • bases that can be used include but are not limited to potassium, sodium, calcium, magnesium, lithium or aluminum hydroxide; potassium, sodium, calcium, magnesium or lithium carbonate or bicarbonate; potassium, sodium, calcium, magnesium, or lithium salts of C1-C5 organic acids; magnesium oxide; ammonia; guanidine carbonate; urea; or combinations thereof.
  • Guanidine carbonate and urea are desirable as they are considered as ashless additives and would be expected to decompose and yield ammonia or ammonia type bases upon exposure to elevated temperatures.
  • the base can be any water soluble nitrogen containing compound that would contribute basicity to the lubricating oil.
  • nitrogen containing compounds would include the amines as defined as components of emulsifiers in the emulsifier' s portion of this application along with salted version of those amines e.g. those amines reacted or partially reacted with mineral acids such as sulfuric acid or low molecular weight organic acids such as acetic acid or maleic acid.
  • mineral acids such as sulfuric acid or low molecular weight organic acids such as acetic acid or maleic acid.
  • formaldehyde or polyalcohol such as tris(hydroxymethyl)aminomethane.
  • the nitrogen containing compound could also be a polyether amine e.g. a poly(alkeneoxide) of low or high molecular weight with one or more terminal amine groups.
  • Preferred bases include NaOH, Ca(OH) 2 , CaCO 3 , KOH, or blends thereof.
  • MgO and Mg(OH) 2 are desirable as some or all of the base in engine lubricant applications where a high amount of vanadium is present in the fuels. They minimize a vanadate problem associated with the vanadium. While KOH was used in the examples other bases are just as preferred.
  • base can be present in almost any amount preferred ranges for marine diesel applications include from about 0.5 to about 30 weight percent based on the weight of the formulated lubricant and more desirably from about 5 to about 30 weight percent.
  • Preferred amounts of base for lubricants for general internal combustion engines are from about 0.1, 0.2, or 0.3 to about 10 or 30 weight percent.
  • the formulated lubricant for marine diesel will desirably have a total base number in excess of 10, 20, 30, 40, or 60 units where a unit is equivalent to one milligram of KOH/gram of formulated lubricant. More desirably the lubricant will have a total base number between 20 and 100 or 150 and preferably between 40 and 100 or 150.
  • TBN values for lubricants for general internal combustion engines are from about 1, 2, or 3 to about 10 or 20.
  • the lubricant will have at least 50% of its total base number contributed by the base that was soluble or dispersible in water or other oil-insoluble solvent.
  • at least 10, 20, or 30 units of TBN will be attributable to the base added to the lubricant with an oil insoluble solvent (e.g. water).
  • the remainder of the total base number may be provided by a variety of overbased oil soluble components such as overbased detergents that are still included in the composition.
  • the base added in this application will be dispersed, often as a dissolved base, in an oil insoluble solvent (e.g. water) that is then emulsified in the oil.
  • the dispersed phase can be present as a dispersed nanoparticle or micron sized particle, if the oil insoluble solvent has been removed.
  • the base or at least the majority of the base will not be solubilized into the oil on a molecular scale.
  • base component according to this invention will not be part of those overbased metal compounds described in patents such as US 2,626,904; 3,626,905; 3,695,910 or 2,739,125 where a first base is added to the oil along with an oil soluble acid or surfactant and then said base is chemically reacted with another chemical, typically a gas such as CO 2 or SO 2 , to form another second different base in situ in the oil phase, said second base having different solubility or dispersibihty in the oil phase due to the method of preparation and the presence of oil soluble acid or surfactant.
  • a first base is added to the oil along with an oil soluble acid or surfactant and then said base is chemically reacted with another chemical, typically a gas such as CO 2 or SO 2 , to form another second different base in situ in the oil phase, said second base having different solubility or dispersibihty in the oil phase due to the method of preparation and the presence of oil soluble acid or surfactant.
  • the base component of this invention will be similar to the overbased metal compounds in that desirably the ratio of equivalents of base to total equivalents of anionic groups on the surfactants will be above 2.5, more desirably above 5, and preferably above 10.
  • Anionic groups on surfactants are well known and include COO " and SO 3 " . These high ratios are indicative that the base in not simply being carried as the counter ion to the surfactant groups.
  • These overbased components formed by in situ chemical reactions may be present as other functional additives in the lubricant and may be formed in trace amounts due to exposure of bases to trace CO 2 in the air.
  • the bases added with the oil insoluble solvents e.g. water
  • the oil insoluble solvents e.g. water
  • the base can become the major or only component in the
  • Dispersed phase stabilized as a colloidal dispersion by the emulsifier.
  • Dispersed phases above 100 microns in any dimension are less preferred in colloidal dispersions because they are harder to stabilize than smaller sized phases and can contribute to haziness.
  • Dispersed phases above 20 microns in size tend to get caught in conventional engine oil filters.
  • Dispersed phases below 5 nanometers in size typically require significantly larger amounts of emulsifier than dispersed phases of
  • the dispersed phases of base and optional oil insoluble solvent desirably has a number average or intensity average particle size by light scattering of 5 nanometers to 100 microns, more desirably from
  • the base in this application is not an alkali or alkaline metal borate or hydrated alkali or alkaline metal borate as described in US 3,853,772 and related patent documents on the use of borate compounds in lubricants.
  • water-soluble refers to materials that are soluble in water to the extent of at least one gram per 100 milliliters of water at 25°C.
  • lubricant or hydrocarbon lubricant soluble refers to materials that are soluble in a SAE 30 paraffinic base oil lubricant to the extent of at least one gram per 100 milliliters of lubricant at 25°C.
  • Hydrocarbyl groups or substituents refers to a group having one or more carbon atoms directly attached to the remainder of the molecule having a hydrocarbon nature or predominantly so and includes 1) pure hydrocarbon groups (e.g. alkyl, alkenyl, alkylene, and cyclic materials), 2) substituted hydrocarbon groups, which are still predominantly hydrocarbon in nature (e.g.
  • heterosubstituted hydrocarbon groups such as described in 2) with no more than 1 or 2 halogen, oxygen, sulfur, or nitrogen atoms or combinations per 10 carbon atoms.
  • the emulsifier used in accordance with the invention is an emulsifier composition which comprises: (i) a hydrocarbon lubricant-soluble product made by reacting a hydrocarbyl substituted carboxylic acid acylating agent with ammonia or an amine, the hydrocarbyl substituent of said acylating agent having about 50 to about 500 carbon atoms; (ii) an ionic or a nonionic compound having a hydrophilic lipophilic balance (HLB) of about 1 to about 30; a mixture of (i) and (ii); or a mixture of (i) and (ii) in combination with (iii) a water-soluble salt distinct from (i) and (ii).
  • HLB hydrophilic lipophilic balance
  • the hydrocarbyl-substituted carboxylic acid acylating agent for the hydrocarbon lubricant-soluble product (i) may be a carboxylic acid or a reactive equivalent of such acid.
  • the reactive equivalent may be an acid halide, anhydride, or ester, including partial esters and the like.
  • the hydrocarbyl substituent for the carboxylic acid acylating agent may contain from about 50 to about 300 or 500 carbon atoms, and in one embodiment about 60 to about 200 carbon atoms.
  • the hydrocarbyl substituent of the acylating agent has a number average molecular weight of about 500 or 750 to about 3000, and in one embodiment about 900 to about 2000 or 2300.
  • the hydrocarbyl-substituted carboxylic acid acylating agent for the hydrocarbon lubricant-soluble product (i) may be made by reacting one or more alpha-beta olefinically unsaturated carboxylic acid reagents containing 2 to about 20 carbon atoms, exclusive of the carboxyl groups, with one or more olefin polymers as described more fully hereinafter.
  • the alpha-beta olefinically unsaturated carboxylic acid reagents may be either monobasic or polybasic in nature. These are disclosed in US '237 column 13.
  • the olefin monomers from which the olefin polymers may be derived are polymerizable olefin monomers characterized by having one or more ethylenic unsaturated groups and they (monomers and polymers) are described in US '237 column 14.
  • polyisobutylenes generally contain predominantly (that is, greater than about 50 percent of the total repeat units) isobutene repeat units of the configuration
  • the olefin polymer is a polyisobutene group (or polyisobutylene group) having a number average molecular weight of about 750 to about 3000, and in one embodiment about 900 to about 2000.
  • the acylating agent for the hydrocarbon lubricant- soluble product (i) is a hydrocarbyl-substituted succinic acid or anhydride represented correspondingly by the formulae
  • R is hydrocarbyl group of about 50 to about 500 carbon atoms, and in one embodiment from about 50 to about 300, and in one embodiment from about 60 to about 200 carbon atoms.
  • the production of these hydrocarbyl-substituted succinic acids or anhydrides via alkylation of maleic acid or anhydride or its derivatives with a halohydrocarbon or via reaction of maleic acid or anhydride with an olefin polymer having a terminal double bond is well known to those of skill in the art and need not be discussed in detail herein.
  • the hydrocarbyl-substituted carboxylic acid acylating agent for the product hydrocarbon lubricant-soluble product (i) is a hydrocarbyl- substituted succinic acylating agent consisting of hydrocarbyl substituent groups and succinic groups.
  • the hydrocarbyl substituent groups are derived from an olefin polymer as discussed above.
  • the hydrocarbyl-substituted carboxylic acid acylating agent is characterized by the presence within its structure of an average of at least 1.3 succinic groups, and in one embodiment from about 1.5 to about 2.5, and in one embodiment form about 1.7 to about 2.1 succinic groups for each equivalent weight of the hydrocarbyl substituent.
  • the hydrocarbyl-substituted carboxylic acid acylating agent is characterized by the presence within its structure of about 1.0 to about 1.3, and in one embodiment from about 1.0 to about 1.2, and in one embodiment from about 1.0 to about 1.1 succinic groups for each equivalent weight of the hydrocarbyl substituent.
  • the hydrocarbyl-substituted carboxylic acid acylating agent is a polyisobutene-substituted succinic anhydride, the polyisobutene substituent having a number average molecular weight of about 1500 to about 3000, and in one embodiment about 1800 to about 2300, said first polyisobutene- substituted succinic anhydride being characterized by about 1.3 to about 2.5, and in one embodiment about 1.7 to about 2.1 succinic groups per equivalent weight of the polyisobutene substituent.
  • the hydrocarbyl-substituted carboxylic acid acylating agent is a polyisobutene-substituted succinic anhydride, the polyisobutene substituent having a number average molecular weight of about 700 to about 1300, and in one embodiment about 800 to about 1000, said polyisobutene-substituted succinic anhydride being characterized by about 1.0 to about 1.3, and in one embodiment about 1.0 to about 1.2 succinic groups per equivalent weight of the polyisobutene substituent.
  • the hydrocarbon lubricant-soluble product (i) may be formed using ammonia and/or an amine.
  • the amines useful for reacting with the acylating agent to form the product (i) include monoamines, polyamines, and mixtures thereof.
  • the monoamines have only one amine functionality whereas the polyamines have two or more.
  • the amines may be primary, secondary or tertiary amines.
  • the primary amines are characterized by the presence of at least one -NH 2 group; the secondary by the presence of at least one H — N ⁇ group.
  • the tertiary amines are analogous to the primary and secondary amines with the exception that the hydrogen atoms in the — NH 2 or H — N ⁇ groups are replaced by hydrocarbyl groups. Examples of primary and secondary monoamines are in US '237 column 16.
  • the amines may be hydroxyamines.
  • the hydroxyamines may be primary, secondary or tertiary amines.
  • the hydroxyamines are primary, secondary or tertiary alkanolamines.
  • the alkanol amines may be represented by the formulae:
  • each R is independently a hydrocarbyl group of 1 to about 8 carbon atoms, or a hydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms and each R' independently is a hydrocarbylene (i.e., a divalent hydrocarbon) group of 2 to about 18 carbon atoms.
  • the amine may be an alkylene polyamine. Especially useful are the linear or branched alkylene polyamines represented by the formula
  • n has an average value between 1 and about 10, and in one embodiment about 2 to about 7, the "Alkylene” group has from 1 to about 10 carbon atoms, and in one embodiment about 2 to about 6 carbon atoms, and each R is independently hydrogen, an aliphatic or hydroxy-substituted aliphatic group of up to about 30 carbon atoms.
  • alkylene polyamines are described in US '237 column 18.
  • Ethylene polyamines are useful.
  • the amine is a polyamine bottoms or a heavy polyamine.
  • polyamine bottoms refers to those polyamines resulting from the stripping of a polyamine mixture to remove lower molecular weight polyamines and volatile components to leave, as residue, the polyamine bottoms.
  • the polyamine bottoms are characterized as having less than about 2% by weight total diethylene triamine or triethylene tetramine. These are described in US '237 column 18.
  • the hydrocarbon lubricant-soluble product (i) may be a salt, an ester, an amide, an imide, or a combination thereof.
  • the salt may be an internal salt involving residues of a molecule of the acylating agent and the ammonia or amine wherein one of the carboxyl groups becomes ionically bound to a nitrogen atom within the same group; or it may be an external salt wherein the ionic salt group is formed with a nitrogen atom that is not part of the same molecule.
  • the amine is a hydroxyamine
  • the hydrocarbyl-substituted carboxylic acid acylating agent is a hydrocarbyl-substituted succinic anhydride
  • the resulting hydrocarbon lubricant-soluble product (i) is a half ester and half salt, i.e., an ester/salt.
  • Component (i)(b) is a hydrocarbon lubricant-soluble product made by reacting an acylating agent with at least one ethylene polyamine such as TEPA (tetraethylenepentamine), PEHA (pentaethylenehexaamine), TETA
  • component (i)(b) is preferably made from a polyisobutylene group having a number average molecular weight of from about 700 to about 1300 and that is succinated in the range from 1.0 up to 1.3.
  • the lubricant soluble product comprises: (i)(a) a first lubricant- soluble product made by reacting a first hydrocarbyl-substituted carboxylic acid acylating agent with ammonia or an amine, the hydrocarbyl substituent of said first acylating agent having about 50 to about 500 carbon atoms; and (i)(b) a second lubricant-soluble product made by reacting a second hydrocarbyl-substituted carboxylic acid acylating agent with ammonia or an amine, the hydrocarbyl substituent of said second acylating agent having about 50 to about 500 carbon atoms.
  • the products (i)(a) and (i)(b) are different.
  • the molecular weight of the hydrocarbyl substituent for the first acylating agent may be different than the molecular weight of the hydrocarbyl substituent for the second acylating agent.
  • the number average molecular weight for the hydrocarbyl substituent for the first acylating agent may be in the range of about 1500 to about 3000, and in one embodiment about 1800 to about 2300
  • the number average molecular weight for the hydrocarbyl substituent for the second acylating agent may be in the range of about 700 to about 1300, and in one embodiment about 800 to about 1000.
  • the first hydrocarbyl-substituted carboxylic acid acylating agent may be a polyisobutene-substituted succinic anhydride, the polyisobutene substituent having a number average molecular weight of about 1500 to about 3000, and in one embodiment about 1800 to about 2300.
  • This first polyisobutene-substituted succinic anhydride may be characterized by at least about 1.3, and in one embodiment about 1.3 to about 2.5, and in one embodiment about 1.7 to about 2.1 succinic groups per equivalent weight of the polyisobutene substituent.
  • the amine used in this first lubricant-soluble product (i)(a) may be an alkanol amine and the product may be in the form of an ester/salt.
  • the second hydrocarbyl-substituted carboxylic acid acylating agent may be a polyisobutene- substituted succinic anhydride, the polyisobutene substituent of said second polyisobutene-substituted succinic anhydride having a number average molecular weight of about 700 to about 1300, and in one embodiment about 800 to about 1000.
  • This second polyisobutene-substituted succinic anhydride may be charac terized by about 1.0 to about 1.3, and in one embodiment about 1.0 to about 1.2 succinic groups per equivalent weight of the polyisobutene substituent.
  • the amine used in this second lubricant-soluble product (i)(b) may be an alkanol amine and the product may be in the form of an ester/salt, or the amine may be an alkylene polyamine and the product may be in the form of a succinimide.
  • the lubricant-soluble product (i) may be comprised of: about 1% to about 99% by weight, and in one embodiment about 30% to about 70% by weight of the product (i)(a); and about 99% to about 1% by weight, and in one embodiment about 70% to about 30% by weight of the product (i)(b).
  • the lubricant soluble product comprises: (i)(a) a first hydrocarbyl-substituted carboxylic acid acylating agent, the hydrocarbyl substituent of said first acylating agent having about 50 to about 500 carbon atoms; and (i)(b) a second hydrocarbyl-substituted carboxylic acid acylating agent, the hydrocarbyl substituent of said second acylating agent having about 50 to about 500 carbon atoms, said first acylating agent and said second acylating agent being the same or different; said first acylating agent and said second acylating agent being coupled together by a linking group derived from a compound having two or more primary amino groups, two or more secondary amino groups, at least one primary amino group and at least one secondary amino group, at least two hydroxy] groups, or at least one primary or secondary amino group and at least one hydroxyl group; said coupled acylating agents being reacted with ammonia or an amine.
  • the molecular weight of the hydrocarbyl substituent for the first acylating agent may be the same as or it may be different than the molecular weight of the hydrocarbyl substituent for the second acylating agent.
  • the number average molecular weight for the hydrocarbyl substituent for the first and/or second acylating agent is in the range of about 1500 to about 3000, and in one embodiment about 1800 to about 2300.
  • the number average molecular weight for the hydrocarbyl substituent for the first and/or second acylating agent is in the range of about 700 to about 1300, and in one embodiment about 800 to about 1000.
  • the first and/or second hydrocarbyl-substituted carboxylic acid acylating agent may be a polyisobutene-substituted succinic anhydride, the polyisobutene substituent having a number average molecular weight of about 1500 to about 3000, and in one embodiment about 1800 to about 2300.
  • This first and/or second polyisobutene- substituted succinic anhydride may be characterized by at least about 1.3, and in one embodiment about 1.3 to about 2.5, and in one embodiment about 1.7 to about 2.1 succinic groups per equivalent weight of the polyisobutene substituent.
  • the first and/or second hydiOcarbyl-substituted carboxylic acid acylating agent may be a polyisobutene-substituted succinic anhydride, the polyisobutene substituent having a number average molecular weight of about 700 to about 1300, and in one embodiment about 800 to about 1000.
  • This first and/or second polyisobutene- substituted succinic anhydride may be characterized by about 1.0 to about 1.3, and in one embodiment about 1.0 to about 1.2 succinic groups per equivalent weight of the polyisobutene substituent.
  • the linking group may be derived from any of the amines or hydroxyamines discussed above having two or more primary amino groups, two or more secondary amino groups, at least one primary amino group and at least one secondary amino group, or at least one primary or secondary amino group and at least one hydroxyl group.
  • the linking group may also be derived from a polyol.
  • the polyol may be a compound represented in US '237 column 20. The ratio of reactants utilized in the preparation of these linked products may be varied over a wide range.
  • first and second acylating agents for each equivalent of each of the first and second acylating agents, at least about one equivalent of the linking compound is used.
  • the upper limit of linking compound is about two equivalents of linking compound for each equivalent of the first and second acylating agents.
  • the ratio of equivalents of the first acylating agent to the second acylating agent is about 4:1 to about 1:4, and in one embodiment about 1.5:1.
  • the first and second acylating agents may be reacted with the linking compound according to conventional ester and/or amide-forming techniques. This normally involves heating acylating agents with the linking compound, optionally in the presence of a normally liquid, .substantially inert, organic liquid solvent/diluent.
  • reaction between the linked acylating agents and the ammonia or amine may be carried out under salt, ester/salt, amide or imide forming conditions using conventional techniques.
  • the hydrocarbon lubricant soluble product (i) may be present in the aqueous hydrocarbon lubricant compositions of the invention at a concentration of about 0.1 to about 15% by weight, and an one embodiment about 0.1 to about 10% by weight, and in one embodiment about 0.1 to about 5% by weight, and in one embodiment about 0.1 to about 2% by weight, and in one embodiment about 0.1 to about 1% by weight, and in one embodiment about 0.1 to about 0.7% by weight.
  • the ionic or nonionic compound (ii) has a hydrophilic lipophilic balance (HLB) in the range of about 1 to about 20 or 30, and in one embodiment about 4 to about 15 or 20.
  • HLB hydrophilic lipophilic balance
  • examples of these compounds are disclosed in McCutcheon's Emulsifiers and Detergents, 1998, North American & International Edition. Pages 1-235 of the North American Edition and pages 1-199 of the International Edition are incorporated herein by reference for their disclosure of such ionic and nonionic compounds having an HLB in the range of about 1 to about 10 or 30. These are set forth in US '237 column 27.
  • the ionic or nonionic compound (ii) is a poly(oxyalkene) compound.
  • the ionic or nonionic compound (ii) is a hydrocarbon lubricant-soluble product made by reacting an acylating agent having about 12 to about 30 carbon atoms with ammonia or an amine.
  • the acylating agent may contain about 12 to about 24 carbon atoms, and in one embodiment about 12 to about 18 carbon atoms. These are set forth in US '237 column 27.
  • the amine may be any of the amines described above as being useful in making the hydrocarbon lubricant-soluble product (i).
  • the product of the reaction between the acylating agent and the ammonia or amine may be a salt, an ester, an amide, an imide, or a combination thereof.
  • the ionic or nonionic compound (ii) is an ester/salt made by reacting hexadecyl succinic anhydride with dimethylethanolamine in an equivalent ratio (i.e., carbonyl to amine ratio) of about 1:1 to about 1:1.5, and in one embodiment about 1:1.35.
  • the ionic or nonionic compound can be the reaction product of a copolymer of an alpha olefin of 3 to 25 carbon atoms with maleic anhydride reacted with an amine (as previously described).
  • One such reaction product would be a copolymer of octadecene with maleic anhydride that is reacted with triethylene- tetramine. It may be desirable to control crosslinking with these multifunctional reactants by having large amounts of carboxylic acids of lower functionality and/or amines of lower functionality present to avoid forming an insoluble product.
  • the ionic or nonionic compound (ii) may be present in the aqueous hydrocarbon fuel compositions of the invention at a concentration of about 0.01 to about 15% by weight, and in one embodiment about 0.01 to about 10% by weight, and one embodiment about 0.01 to about 5% by weight, and in one embodiment about 0.01 to about 3% by weight, and in one embodiment about 0.1 to about 1% by weight.
  • the water-soluble salt (iii) may be any material capable of forming positive and negative ions in an aqueous solution that does not interfere with the other additives. These include organic amine nitrates, nitrate esters, azides, nitramines, and nitro compounds. Also included are alkali and alkaline earth metal carbonates, sulfates, sulfides, sulfonates, and the like.
  • amine or ammonium salts represented by the formula k[G(NR 3 ) y ] + nX p - wherein G is hydrogen or an organic group of 1 to about 8 carbon atoms, and in one embodiment 1 to about 2 carbon atoms, having a valence of y; each R independently is hydrogen or a hydrocarbyl group of 1 to about 10 carbon atoms, and in one embodiment 1 to about 5 carbon atoms, and in one embodiment 1 to about 2 carbon atoms; X p" is an anion having a valence of p; and k, y, n and p are independently integers of at least 1. When G is H, y is 1.
  • X is a nitrate ion; and in one embodiment it is an acetate ion.
  • Examples include ammonium nitrate, ammonium acetate, methylammonium nitrate, methylammonium acetate, ethylene diamine diacetate, urea nitrate, urea, guanidinium nitrate, and urea dinitrate. Ammonium nitrate is particularly useful.
  • the water-soluble salt (iii) functions as an emulsion stabilizer, i.e., it acts to stabilize the aqueous hydrocarbon lubricant compositions.
  • the water soluble salt may be present in the water- lubricant emulsion at a concentration of about 0.001 to about 1 % by weight, and in one embodiment from about 0.01 to about 1% by weight.
  • the water soluble salt is absent or serves as a different component, such as the water soluble or water dispersible base.
  • a detergent is an additive that reduces formation of piston deposits, for example high- temperature varnish and lacquer deposits, in engines; it normally has acid-neutralizing properties and is capable of keeping finely divided solids in suspension.
  • Most detergents are based on metal "soaps", that is metal salts of acidic organic compounds, these are sometimes referred to as surfactants.
  • Detergents generally comprise a polar head with a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound.
  • the detergents in this invention can be low TBN ( ⁇ 200 mgKOH/g) in which the surfactants are neutralized with base to form metal soaps.
  • they can be overbased detergents in which large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle.
  • the overbased detergents of this invention may have a TBN of at least 200, preferably at least 250, especially at least 300, such as up to 600.
  • Surfactants that may be used include sulfonates, phenates, sulfurized phenates, salicylates, calixarates, salicylic calixarenes, glyoxylates, saligenins, thiophosphonates, naphthenates, other oil-soluble carboxylates, or mixtures of any of these surfactants. Sulfurized phenates are preferred.
  • the metal may be an alkali or alkaline earth metal, e.g., sodium, potassium, lithium, calcium, and magnesium. Calcium is preferred.
  • Surfactants for the surfactant system of the overbased metal compounds preferably contain at least one hydrocarbyl group, for example, as a substituent on an aromatic ring.
  • hydrocarbyl as used herein means that the group concerned is primarily composed of hydrogen and carbon atoms and is bonded to the remainder of the molecule via a carbon atom, but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the group.
  • hydrocarbyl groups in surfactants for use in accordance with the invention are aliphatic groups, preferably alkyl or alkylene groups, especially alkyl groups, which may be linear or branched. The total number of carbon atoms in the surfactants should be at least sufficient to impart the desired oil-solubility.
  • overbased salts can be of oil-soluble organic sulfur acids such as sulfonic, sulfamic, thiosulfonic, sulfinic, sulfonic, partial ester sulfuric, sulfurous and thiosulfuric acid.
  • oil-soluble organic sulfur acids such as sulfonic, sulfamic, thiosulfonic, sulfinic, sulfonic, partial ester sulfuric, sulfurous and thiosulfuric acid.
  • carbocylic sulfonic acids include the mono- or poly-nuclear aromatic or cycloaliphatic compounds.
  • the oil-soluble sulfonates can be represented for the most part by the following formulae:
  • M is either a metal cation as described hereinabove or hydrogen
  • T is a cyclic nucleus such as, for example, benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenyl amine, cyclohexane, petroleum naphthenes, decahydro-naphthalene, cyclopentane, etc.
  • R 11 in Foraiula XIN is an aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl, etc.
  • x is at least 1
  • (R n ) x -T contains a total of at least about 15 carbon atoms
  • R 12 in Formula XV is an ali
  • R 12 radical examples include alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc.
  • R 12 examples include groups derived from petrolatum, saturated and unsaturated paraffin wax, and polyolefins, including polymerized C 2 , C 3 , C 4 , C 5 , C 6 , etc., olefins containing from about 15 to 7000 or more carbon atoms.
  • the groups T, R 11 and R 12 in the above formulae can also contain other inorganic or organic substituents in addition to those enumerated above such as, for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide, etc.
  • substituents for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide, etc.
  • x, y, z and b are at least 1
  • Formula a, b and d are at least 1.
  • sulfonic acids useful in this invention are mahogany sulfonic acids; bright stock sulfonic acids; sulfonic acids derived from lubricating oil fractions having a Saybolt viscosity from about 100 seconds at 100°F.
  • aliphatic sulfonic acids such as paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, hexapropylene sulfonic acids, tetra-amylene sulfonic acids, polyisobutene sulfonic acids wherein the polyisobutene contains from 20 to 7000 or more carbon atoms, chloro-substituted paraffin wax sulfonic acids, nitroparaffin wax sulfonic acids, etc.; cycloaliphatic sulfonic acids such as petroleum naphthene sulfonic acids, cetyl cyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, bis- (di-isobutyl) cyclohexyl sulfonic acids, etc
  • petroleum sulfonic acids or “petroleum sulfonates” includes all sulfonic acids or the salts thereof derived from petroleum products.
  • a particularly valuable group of petroleum sulfonic acids are the mahogany sulfonic acids (so called because of their reddish-brown color) obtained as a by-product from the manufacture of petroleum white oils by a sulfuric acid process.
  • metal ratio is used to designate the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the salt which would be expected to result in the reaction between the organic acid to be overbased and the basic reacting metal compound according to the known chemical reactivity and stoichiometry of the two reactants.
  • metal ratio in a normal or neutral salt the metal ratio is one and, in an overbased salt, the metal ratio is greater than one.
  • the overbased salts usually have metal ratios of at least 1.1:1. Typically they have ratios of 2:1 or 3:1 to 40:1. Salts having ratios of 12:1 to 20:1 are often used.
  • the basically reacting metal compounds used to make the overbased salts are usually an alkali or alkaline earth metal compound (i.e., the Group LA, UA, and LLB metals, but normally excluding francium and radium and typically also excluding rubidium, cesium and beryllium), although other basically reacting metal compounds can be used.
  • alkali or alkaline earth metal compound i.e., the Group LA, UA, and LLB metals, but normally excluding francium and radium and typically also excluding rubidium, cesium and beryllium
  • Compounds of Ca, Ba, Mg, Na and Li, such as their hydroxides and alkoxides of lower alkanols are usually used as basic metal compounds in preparing these overbased salts but others can be used as shown by the prior art refeixed to herein.
  • Overbased salts containing a mixture of ions of two or more of these metals can be used in the present invention.
  • Overbased materials are generally prepared by reacting an acidic material
  • an inorganic acid or lower carboxylic acid, such as carbon dioxide with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter.
  • a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter.
  • the acidic organic compound will, in the present instance, be the functionalize alkyl phenol.
  • the acidic material used in preparing the overbased material can be a liquid such as formic acid, acetic acid, nitric acid, or sulfuric acid. Acetic acid is particularly useful. Inorganic acidic materials can also be used, such as HCI, SO 2 ,
  • CO 2 SO 3 , CO 2 , or H 2 S, and in one embodiment, CO 2 or mixtures thereof, e.g., mixtures of CO 2 and acetic acid.
  • a promoter is a chemical employed to facilitate the incorporation of metal into the basic metal compositions.
  • the promoters are diverse and are well known in the art and include lower alcohols. A discussion of suitable promoters is found in
  • Patents specifically describing techniques for making basic salts of acidic organic compounds generally include U.S. Patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,3 18,809;
  • Phenate surfactants for use in this invention may be non-sulfurized or, preferably, sulfurized.
  • phenate includes those containing more than one hydroxyl group (for example, from alkyl catechols) or fused aromatic rings (for example, alkyl naphthols) and those which have been modified by chemical reaction, for example, alkylene-bridged and Mannich base-condensed and saligenin- type (produced by the reaction of a phenol and an aldehyde under basic conditions).
  • phenols on which the phenate surfactants are based may be derived from the formula I below:
  • R represents a hydrocarbyl group and y represents 1 to 4. Where y is greater than 1, the hydrocarbyl groups may be the same or different
  • Sulfurized hydrocarbyl phenols may typically be represented by the formula 11 below:
  • hydrocarbyl groups represented by R are advantageously alkyl groups, which advantageously contain 5 to 100, preferably 5 to 40, especially 9 to 12, carbon atoms, the average number of carbon atoms in all of- the R groups being at least about 9 in order to ensure adequate solubility in oil.
  • Prefened alkyl groups are dodecyl (tetrapropylene) groups.
  • hydrocarbyl-substituted phenols will for convenience be referced to as alkyl phenols.
  • a sulfurizing agent for use in preparing a sulfurized phenol or phenate may be any compound or element which Introduces -(S)x- bridging groups between the alkyl phenol monomer groups, wherein x is generally from 1 to about 4.
  • the reaction may be conducted with elemental sulfur or a halide thereof, for example, sulfur dichloride or, more preferably, sulfur monochloride. If elemental sulfur is used, the sulfurization reaction may be effected by heating the alkyl phenol compound at from 50 to 250, preferably at least 100°C. The use of elemental sulfur will typically yield a mixture of bridging groups -(S)X- as described above.
  • the sulfurization reaction may be effected by treating the alkyl phenol at from -10 to 120, preferably at least 60°C.
  • the reaction may be conducted in the presence of a suitable diluent.
  • the diluent advantageously comprises a substantially inert organic diluent, for example mineral oil or an alkane.
  • the reaction is conducted for a period of time sufficient to effect substantial reaction. It is generally preferred to employ from 0.1 to 5 moles of the alkyl phenol material per equivalent of sulphurizing agent.
  • sulfurizing agent it may be desirable to use a basic catalyst, for example, sodium hydroxide or an organic amine, preferably a heterocyclic amine (e.g., morpholine).
  • a basic catalyst for example, sodium hydroxide or an organic amine, preferably a heterocyclic amine (e.g., morpholine).
  • sulfurized alkyl phenols useful in preparing overbased metal compounds generally comprise diluent and unreacted alkyl phenols and generally contain from 2 to 20, preferably 4 to 14, most preferably 6 to 12, mass % of sulfur, based on the mass of the sulfurized alkyl phenol.
  • phenol as used herein includes phenols which have been modified by chemical reaction with, for example, an aldehyde, and Mannich base-condensed phenols.
  • Aldehydes with which phenols may be modified include, for example, formaldehyde, propionaldlehyde and butyraldehyde.
  • the preferred aldehyde is formaldehyde.
  • Aldehyde-modified phenols suitable for use are described in, for example, US-A-5 259 967.
  • Mannich base-condensed phenols are prepared by the reaction of a phenol, an aldehyde and an amine. Examples of suitable Mannich base-condensed phenols are described In GB-A-2 121 432.
  • the phenols may include substituents other than those mentioned above provided that such substituents do not detract significantly from the surfactant properties of the phenols. Examples of such substituents are methoxy groups and halogen atoms.
  • the functionalization of the alkyl phenol can comprise the addition of any functional group to the phenolic compound, other than an additional hydroxy group or an additional hydrocarbyl group, at least one such alkyl or hydrocarbyl group already being present in sufficient amount to provide oil solubility to the detergent.
  • Typical functional groups include t-butyl groups, methylene coupling groups, ester- substituted alkyl groups, and aldehyde groups.
  • the functionalization is by addition of carboxy functionality, in which case the detergent can be an alkyl salicylate or a derivative thereof.
  • Salicylate detergents are well known; see, for instance, U.S. Patent 5,688,751 or 4,627,928.
  • the substituent can be based on a glyoxylic acid condensation.
  • a typical glyoxylate condensation product is shown here as an anionic species, which will typically be neutralized with a metal salt.
  • the R groups are alkyl groups.
  • the material shown would be the condensation of 2 moles of alkyl phenol with 1 mole of glyoxylic acid or derivative thereof. Other molar ratios are also possible; when a 1:1 ratio is approached, the condensation product becomes oligomeric or polymeric. These materials and methods for their preparation are disclosed in greater detail in U.S. Patent 5,356,546.
  • the functionalized alkyl phenol can be a condensation product of the alkyl phenol with formaldehyde or other lower aldehydes.
  • the acidic substituent in this case, would be considered to be the one or more additional phenolic groups.
  • the simplest such condensation product would be
  • oligomeric structures can be formed when the molar ratio of formaldehyde:phenol increases.
  • examples of such type of oligomeric species are the calixarates, which are cyclic materials containing 4 to 8 phenol- formaldehye repeat units. Calixarates and methods of their preparation are disclosed in greater detail in U.S. Patent 5,114,601. As will be apparent, mixtures of formaldehyde, other aldehydes, and glyoxylic acid can also be employed in such condensation reactions.
  • Saligenin itself, also known as salicyl alcohol and o- hydroxybenzyl alcohol, is represented by the structure
  • Useful saligenin derivatives include certain metal saligenin derivative which function as detergents. When the metal is magnesium, these compounds can be represented by the formula
  • Mg represents a valence of a magnesium ion, and n, in each instance, is 0 or 1. (When n is zero the Mg is typically replaced by H to form an -OH group.)
  • the value for "m” is typically 0 to 10, so number of such rings will be 1 to 11, although it is to be understood that the upper limit of "m” is not a critical variable. In one embodiment m is 2 to 9, such as 3 to 8 or 4 to 6.
  • Other metals include alkali metals such as lithium, sodium, or potassium; alkaline earth metals such as calcium or barium; and other metals such as copper, zinc, and tin.
  • R 1 which is the aforementioned hydrocarbyl group, such as alkyl group.
  • R 1 can contain 1 to 60 carbon atoms, such as 7 to 28 carbon atoms or 9 to 18 carbon atoms.
  • R 1 will normally comprise a mixture of various chain lengths, so that the foregoing numbers will normally represent an average number of carbon atoms in the R 1 groups (number average).
  • Each ring in the structure will be substituted with 0, 1, 2, or 3 such R 1 groups (that is, p is 0, 1, 2, or 3), most typically 1, and of course different rings in a given molecule may contain different numbers of such substituents.
  • At least one aromatic ring in the molecule must contain at least one R 1 group, and the total number of carbon atoms in al] the R 1 groups in the molecule should be at least 7, such as at least 12.
  • the X and Y groups may be seen as groups derived from formaldehyde or a formaldehyde source, by condensative reaction with the aromatic molecule.
  • the relative amounts of the various X and Y groups depends to a certain extent on the conditions of synthesis of the molecules. While various species of X and Y may be present in the molecules in question, the commonest species comprising X are -CHO (aldehyde functionality) and -CH 2 OH (hydroxymethyl functionality); similarly the commonest species comprising Y are -CH 2 - (methylene bridge) and -CH 2 OCH 2 - (ether bridge).
  • the relative molar amounts of these species in a sample of the above material can be determined by 1H/ 13 C NMR as each carbon and hydrogen nucleus has a distinctive environment and produces a distinctive signal.
  • the signal for the ether linkage, -CH 2 OCH 2 - must be corrected for the presence of two carbon atoms, in order to arrive at a correct calculation of the molar amount of this material. Such a correction is well within the abilities of the person skilled in the art.
  • X is at least in part -CHO and such -CHO groups comprise at least 10, 12, or 15 mole percent of the X and Y groups. In another embodiment the -CHO groups comprise 20 to 60 mole percent of the X and Y groups, such as 25 to 40 mole percent of the X and Y groups.
  • X is at least in part -CH OH and such -CH 2 OH groups comprise 10 to 50 mole percent of the X and Y groups, such as 15 to 30 mole percent of the X and Y groups.
  • Y is at least in part -CH 2 - and such -CH 2 - groups comprise 10 to 55 mole percent of the X and Y groups, such as 25 to 45 or 32 to 45 mole percent of the X and Y groups.
  • Y is at least in part -CH 2 OCH 2 - and such -CH 2 OCH 2 - groups comprise 5 to 20 mole percent of the X and Y groups, such as 10 to 16 mole percent of the X and Y groups.
  • the above-described compound is, as mentioned, typically a magnesium salt and, indeed, the presence of magnesium during the preparation of the condensed product is believed to be useful in achieving the desired ratios of X and Y components described above.
  • the number of Mg ions in the compound is characterized by an average value of "n" of 0.1 to 1 throughout the composition, such as 0.2 or 0.3 to 0.4 or 0.5, or 0.35 to 0.45. Since Mg is normally a divalent ion, when all of the phenolic structures shown are entirely neutralized by Mg +2 ions, the average value of n in the composition will be 0.5, that is, each Mg ion neutralizes 2 phenolic hydroxy groups. Those two hydroxy groups may be on the same or on different molecules.
  • n is less than 0.5, this indicates that the hydroxy groups are less than completely neutralized by Mg ions. If the value of n is greater than 0.5, this indicates that a portion of the valence of the Mg ions is satisfied by an anion other than the phenolic structure shown. For example each Mg ion could be associated with one phenolic anion and one hydroxy (OH ⁇ ) ion, to provide an n value of 1.0.
  • n is 0.1 to 1.0 is not directly applicable to overbased versions of this material (described below and also a part of the present invention) in which an excess of Mg or another metal can be present.
  • the above-described component can be prepared by combining a phenol substituted by the above-described R 1 group with formaldehyde or a source of formaldehyde and magnesium oxide or magnesium hydroxide under reactive conditions, in the presence of a catalytic amount of a strong base.
  • formaldehyde includes paraformaldehyde, trioxane, and formalin .
  • paraformaldehyde is can be used.
  • the relative molar amounts of the substituted phenol and the formaldehyde can be important in providing products with the desired structure and properties.
  • the substituted phenol and formaldehyde are reacted in equivalent ratios of 1:1 to 1:3 or 1.4, such as 1:1.1 to 1:2.9 or 1:1.4 to 1:2.6, or 1:1.7 to 1:2.3.
  • One equivalent of formaldehyde is considered to correspond to one H 2 CO unit; one equivalent of phenol is considered to be one mole of phenol.
  • the strong base can be sodium hydroxide or potassium hydroxide, and can be supplied in an aqueous solution.
  • the process can be conducted by combining the above components with an appropriate amount of magnesium oxide or magnesium hydroxide with heating and stirring.
  • a diluent such as mineral oil or other diluent oil can be included to provide for suitable mobility of the components.
  • An additional solvent such as an alcohol can be included if desired, although it is believed that the reaction may proceed more efficiently in the absence of additional solvent.
  • the reaction can be conducted at room temperature or at a slightly elevated temperature such as 35-120°C, 70-110°C, or 90-100°C, and of course the temperature can be increased in stages. When water is present in the reaction mixture it is convenient to maintain the mixture at or below the normal boiling point of water.
  • the mixture can be heated to a higher temperature, typically under reduced pressure, to strip off volatile materials.
  • a suitable time e.g., 30 minutes to 5 hours or 1 to 3 hours
  • the mixture can be heated to a higher temperature, typically under reduced pressure, to strip off volatile materials.
  • the final temperature of this stripping step is 100 to about 150°C, such as 120 to about 145°C.
  • Reaction under the conditions described above typically leads to a product which has a relatively high content of -CHO substituent groups, that is, 10%, 12%, and even 15% and greater.
  • Such materials when used as detergents in lubricating compositions, exhibit good upper piston cleanliness performance, low Cu/Pb corrosion, and good compatibility with seals.
  • Use of metals other than magnesium in the synthesis typically leads to a reduction in the content of -CHO substituent groups.
  • Salicylate surfactants used in accordance with the invention may be non- sulfurized or sulfurized, and may be chemically modified and/or contain additional substituents, for example, as discussed below for phenates. Processes similar to those described below may also be used for sulfurizing a hydrocarbyl-substituted salicylic acid, and are well known to those skilled in the art. Salicylic acids are typically prepared by the carboxylation, by the Kolbe-Schmit process, of phenoxides, and in that case, will generally be obtained (normally in a diluent) in admixture with uncarboxylated phenol. Calixarates such as salixarenes i.e.
  • salicylic calixarenes are also useful compounds to add as surfactants to lubricating oils.
  • Salicylic calixarenes useful in this invention include those described in US Patent 6,200,936B1 to the Lubrizol Corporation hereby incorporated by reference for its teachings.
  • Preferred substituents in oil-soluble salicylic, acids from which salicylates in accordance with the invention may be derived are the substituents represented by R in the discussion below of phenols.
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 12 to 20, carbon atoms.
  • Oil of Lubricating Viscosity The lubricating oils used may vary significantly depending on the final use of the oil. SAE 5 or 10 to about 70 are typical of the oils used in various internal combustion engines of various designs. Marine diesel applications typically call for the higher viscosity oils to provide a thicker lubricating film. While multigrade oils are desirable where the oil needs to provide lubrication at higher use temperatures along with low energy consumption at cold starting temperatures, marine diesel applications tend to use a single grade oil because the engines are subject to minimal cycling on and off and run for extended periods of time when operational. If a multigrade oil is used, desirably it has a viscosity index of at least 90, more desirably at least 100 and preferably at least 110.
  • the lubricating oil basestock for marine diesel applications has a kinematic viscosity at 100 C (as measured by ASTM D445) of at least 14 centistokes, preferably at least 15 centistokes, more preferably in the range of from 17 to 30 centisokes, for example from 17 to 25 centistokes.
  • the lubricating oil can be any conventional oil or blends thereof used in internal combustion engines for a lubricant.
  • the oil is a petroleum derived lubricating oil (e.g. distillation products), such as a naphthenic base, paraffinic base or a mixed base oil.
  • the lubricant depending on the application be a blend of petroleum derived oils and synthetic oils.
  • the lubricating oil may be a synthetic oil such as synthetic ester lubricating oils.
  • Other lubricating oils that can be used are hydrocracked oils where the refining process further breaks down the middle and heavy distillate fractions in the presence of hydrogen. Liquid alpha olefin polymers may also be part or all of the lubricant.
  • Fischer-Tropsch oils can be used in the lubricant.
  • Brightstock typically characterized as solvent- extracted, de-asphalted products from vacuum residuum, typically having a kinematic viscosity at 100 C of from 28- 36 centistokes may also be used.
  • the lubricant of the invention also can include conventional additives like detergents, dispersants, viscosity modifiers, antioxidants, extreme pressure additives (antiwear additives), foam inhibitors, corrosion inhibitors, etc. that are well known to the lubricant art. These additives can be used in conventional amounts.
  • the lubricant of the invention contains an antifreeze agent to prevent freezing of the water component.
  • the antifreeze agent is typically an alcohol. Examples include but are not limited to ethylene glycol, propylene glycol, methanol, ethanol, glycerol and mixtures of two or more thereof.
  • the antifreeze agent is typically used at a concentration sufficient to prevent freezing of the water used in the lubricant. The concentration is therefore dependent upon the temperature at which the lubricant is stored or used. In one embodiment, the concentration is at a level of up to about 20% by weight based on the weight of the water-fuel emulsion, and in one embodiment about 0.1 to about 20% by weight, and in one embodiment about 0.2 to about 10% by weight.
  • water soluble bases such as KOH in a lubricating oil does not result in any significant instability problems for the bases when the temperature of the oil exceeds 100°C where the water may be evaporating at a fairly rapid rate and the total amount of water may be significantly less than the amount in the formulation.
  • Marine cylinder lubricants are used in marine engines including two stroke marine engines in order to provide lubricity, antioxidancy, high temperature detergency and neutralisation of sulphuric acid formed during the combustion.
  • Traditional formulations use overbased detergents for acid neutralisation.
  • the following examples describe a water in lubricant oil emulsion, which uses KOH dissolved in the water phase. KOH is a widely used and non-expensive base. KOH could neutralise the acids formed during the combustion in a more efficient way than the overbased detergents, which would improve the efficiency of the marine cylinder lubricant and reduce the cost of the formulation.
  • the examples also describe the emulsifiers used for the preparation of the water in oil emulsion. These emulsifiers could also contribute to the high temperature detergency. Examples
  • Oil in oil emulsions containing -20 %w/w KOH aqueous solution (35 %KOH w/w) and ⁇ 80%w/w oil formulation were prepared.
  • the oil formulation contains 1 - 2 %w/w emulsifying surfactants, ⁇ 2% w/w dispersant, ⁇ 3 %w/w antioxidant, ⁇ l%w/w aliphatic solvent and 92 - 93 % w/w SAE-50 oil.
  • the emulsifiers play an important role in the emulsion preparation and storage stability.
  • the first emulsifier of a blend of two emulsifiers used to prepare the examples was a PLBSA:EG:DMEA, polyisobutenyl succinic anhydride:ethylene glycol :dimethyl ethanol amine - 2:1:2 (eq).
  • This emulsifier has a high molecular weight polyisobutylene chain (-1500MW) and a low HLB.
  • Emulsifier two was a co- emulsifier.
  • HDSA:DMEA dodecahexylene succinic anhydride: dimethyl ethanol amine 1:1 (eq.) It has a low molecular weight and a high HLB.
  • the structures of these two emulsifiers are presented below.
  • Emulsifiers used in the laboratory manufacture of water/marine lubricating oil emulsion are used in the laboratory manufacture of water/marine lubricating oil emulsion.
  • the emulsifiers can be either dosed through an emulsifying concentrate or could be directly dissolved in the SAE-50 oil. Other emulsifiers could be used for the preparation of water/marine lubricating oil emulsions.
  • the water/marine lubricating oil emulsion generally also contain a dispersant, like PLBSA:TEPA, a polyisobutenyl succinic anhydride:tetraethylene pentaamine -3:1 eq and an antioxidant, like calcium dodecyl phenate sulphide.
  • a dispersant like PLBSA:TEPA
  • an antioxidant like calcium dodecyl phenate sulphide.
  • Table 1 An example of emulsion composition is presented in Table 1.
  • the potassium hydroxide solution is prepared by dissolving 35 g KOH pellets into 75 g of deionised water. This solution is not saturated. Synthetic sea- water can be used instead of deionised water (prepared as per ASTM D665-98) but then the solution becomes saturated at this concentration of KOH.
  • the water/marine lubricating oil emulsions can be prepared either i) via a concentrate, which contains a solvent and two emulsifiers or ii) via a method which uses the solvent and emulsifiers dissolved in the oil. Initial samples were prepared via a concentrate while later samples were prepared using a solvent and the emulsifier dissolved in the oil.
  • An emulsifying concentrate was prepared by mixing the two surfactants with a suitable aliphatic solvent. This concentrate was then mixed until homogeneous with the oil, which contains a dispersant and an antioxidant. The concentrate + oil mixture were weighed into a beaker to which KOH solution was added. The mixture was then sheared for 3 - 6 minutes using a high shear device, such as a Silverson or a Turrax mixer.
  • a high shear device such as a Silverson or a Turrax mixer.
  • the emulsifying surfactants and aliphatic solvent can be mixed with the oil, dispersant and anti-oxidant to forni an oil formulation. This oil formulation is weighed into a beaker to which KOH solution is added. The mixture is then sheared for 3 - 6 minutes using a high shear device, such as a Silverson or a Turrax mixer.
  • Emulsion Stability Water/marine lubricating oil emulsions were stored at room temperature and 65 °C in order to assess their stability against separation into a water phase and an oil phase over time. Stability was assessed after 7 days at room temperature, 7 days at 65°C, 28 days at room temperature and 28 days at 65°C. Emulsion stability was semi-quantitatively evaluated by %v/v separation of oil, oily emulsion, band and water. The presence of a separated water phase is considered particularly detrimental. Examples for emulsion stability are shown below. The emulsion ratings are reported after 7 and 28 days at room temperature and 65°C.
  • This test cell consists of a heater finger, which can be heated up to 350°C using an Eurotherm. A stainless steel panel fitted on the heater finger. The panel and heater finger are placed in a glass cell. The formulation to be tested was dosed at 5 the required rate onto the heated panel with the help of a small tube attached to a peristaltic pump.
  • DI deionised water
  • Beaker Neutralization 75.15 g of water/lubricant oil emulsion was weighed in a beaker. 2.25 g of sulfuric acid (96 % w/w) was then added to the beaker. The mixture was sheared for 5 minutes using a high shear Turrax mixer set up at 24000 rpm. The TBN of the water/lubricant oil emulsion was measured before and after the test. This test was repeated using the standard marine cylinder lubricant described in Table 7. Table 5 presents the results of the beaker neutralization test. It can be seen that the efficiency of water/lubricant oil emulsion in neutralizing sulfuric acid is comparable to the efficiency of the standard oil in neutralizing sulfuric acid. Table 5: Beaker Neutralization Test Results
  • DI deionised water
  • the test set-up shown in Figure 4 was used for assessing the efficiency of water/lubricant oil emulsions in neutralizing sulfuric acid at hot temperatures.
  • the panel was heated to 100°C. As soon as this temperature was reached, the flow of water/lubricant oil emulsion was started through Inlet 1 at 1.67 ml/min. When the emulsion covered the panel, the flow of sulfuric acid was started through Inlet 2 at 0.05 ml/min.
  • the water/lubricant oil emulsion was dosed through a 1 mm bore size tube connected to a peristaltic pump, whereas the acid was dosed through a fine needle (21Gx35 mm), with the help of a syringe pump.
  • the experiment was repeated at 200 °C.
  • the standard oil was also assessed at 100 and 200 °C. The results of these tests are described in Table 6:
  • the aim of this test was to mimic a real situation when the lubricating oil meets the sulfuric acid, formed during the combustion, on the surface of the hot metal cylinder walls.
  • the result from Table 6 illustrates that neutralization of sulfuric acid by the emulsion or by the standard oil was minimal at 100°C. At 200°C the emulsion and the standard oil partially neutralized the sulfuric acid.
  • Bolnes is a turbocharged, 3 cylinder, 2 stroke, low speed marine diesel engine.
  • the Bolnes engine test allows the simultaneous testing of three different cylinder oils over a 72 hour period.
  • each cylinder lubricant is tested in turn in each cylinder of the engine.
  • Several parameters are rated/measured in this test. The most important ones are cleanliness ratings, piston ring wear, cylinder liner wear and analyses of the cylinder drain samples. The piston ring grooves, lands and skirt and the scavenging port clogging are rated for cleanliness. The weight loss of the rings is recorded as a measure of piston ring wear.
  • the cylinder drain samples are analyzed for TBN, TAN, ICP/AES, KV100.
  • Emulsion lubricant was tested in a Bolnes engine test, which only used one lubricant/cylinder (72 hour test). Cylinder 1 used an emulsion lubricant at 100 % treat rate, cylinder 2 used a standard marine cylinder lubricant and cylinder 3 used an emulsion lubricant at 125 % treat rate. The reason for testing an emulsion lubricant at 125 % treat rate was to allow a fairer comparison between the standard lubricant and emulsion lubricant. Emulsion lubricant is composed of 80 % w/w oil phase, hence at 100 % treat rate it will deliver less oil than the standard marine cylinder lubricant.
  • emulsion lubricant delivers 100 % oil, allowing for a fairer comparison between emulsion lubricant and the standard marine cylinder lubricant.
  • the composition of the tested emulsions and the standard marine cylinder lubricant are presented in Table 7.
  • the TBN decreased until it reached equilibrium.
  • This equilibrium was reached after ⁇ 36 hours in drain oils from the cylinders, which used emulsion lubricant and after -60 hours in the drain oils from the cylinders, which used standard mcl. This might indicate a more efficient neutralization of the sulphur oxidation products achieved by emulsion lubricant than by the standard mcl.
  • the TAN of the drain oil samples increased in time until it reached equilibrium. The equilibrium was achieved after ⁇ 36 hours in the cylinders, which used emulsion lubricant and after ⁇ 60 hours in the cylinder, which used the standard mcl.
  • Table 8 summarizes the wear metal content of the drain oil samples at time zero and at the end of the test.
  • the drain oil sample from cylinder 2 contained more iron, copper, nickel and chromium than the drain oil samples from cylinders 1 and 3.
  • Table 9 presents the results of the piston ratings. Overall, the piston ratings show an equivalent or in some cases better performance from the emulsion lubricant than from the standard mcl.
  • Table 10 presents the ratings of the liner and air inlet port blockage. Overall the emulsion lubricant performed better than the standard mcl. The emulsion lubricant did not cause quill deposits and air inlet ports deposits and formed fewer deposits on the liners than the standard mcl. Co ⁇ osion was noticed on the liner of the cylinder, which run on the standard mcl and this was not noticed on the liners of the cylinders, which run on emulsion lubricant.
  • the emulsion lubricant resulted in improved properties over the standard marine cylinder lubricant in tests for piston ring groove carbon, piston ring land carbon, piston ring weight loss, corrosive wear, liner diameter increase, fire land and quill deposits, and air inlet blockage.
  • the emulsion lubricant resulted in comparable properties for the ring stick and adhesive wear.
  • the treat rate with the emulsion lubricant of this disclosure may be less than the treat rate with standard marine cylinder lubricants.
  • the emulsion lubricants are compatible with standard marine cylinder lubricants and could be blended to obtain optimal properties and to reduce costs.
  • the water in the marine emulsion lubricant will lower the combustion temperature in the cylinders slightly and thereby reduce the NOx emissions of the engine.
  • the amount of NOx reduction will be determined by the total amount of water injected with the emulsion lubricant.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne un lubrifiant se présentant sous la forme d'un solvant insoluble dans l'huile, par ex. une émulsion eau dans l'huile, une base soluble dans l'eau ou dispersible dans l'eau étant présente dans la phase dispersée. Ces lubrifiants présentent des avantages lorsqu'ils sont appliqués dans différents domaines tels que dans les moteurs à combustion interne où l'huile utilisée doit avoir une basicité suffisante pour neutraliser tout acide minéral produit par le soufre présent dans le carburant.
PCT/US2002/020394 2001-06-29 2002-06-27 Lubrifiant comprenant une base dispersible dans l'eau WO2003002697A1 (fr)

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JP2003509060A JP2004531638A (ja) 2001-06-29 2002-06-27 水分散性塩基を含有する潤滑剤
US10/482,529 US20040248747A1 (en) 2001-06-29 2002-06-27 Lubricant including water dispersible base
CA002451220A CA2451220A1 (fr) 2001-06-29 2002-06-27 Lubrifiant comprenant une base dispersible dans l'eau
EP02747990A EP1404786A1 (fr) 2001-06-29 2002-06-27 Lubrifiant comprenant une base dispersible dans l'eau

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US30218001P 2001-06-29 2001-06-29
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US34273401P 2001-12-20 2001-12-20
US60/342,734 2001-12-20

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014033634A3 (fr) * 2012-08-29 2014-04-17 Indian Oil Corporation Limited Additif de lubrifiant et compositions d'huile de lubrifiant et leur procédé de préparation
EP3495462A1 (fr) * 2017-12-11 2019-06-12 Infineum International Limited Compositions neutralisant les acides à faible teneur en cendres et sans cendres et compositions d'huile lubrifiante les contenant

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EP1692249B1 (fr) * 2003-12-12 2010-02-24 The Lubrizol Corporation Composition lubrifiante contenant de dispersants succinimide
ES2422217T3 (es) * 2005-03-01 2013-09-09 Solberg Scandinavian As Concentrado de espuma para apagar incendios
JP5784756B2 (ja) * 2011-02-09 2015-09-24 ザ ルブリゾル コーポレイションＴｈｅ Ｌｕｂｒｉｚｏｌ Ｃｏｒｐｏｒａｔｉｏｎ アスファルテン分散剤含有潤滑組成物
CA2831839A1 (fr) 2011-03-29 2012-10-04 Fuelina Technologies, Llc Combustible hydride et son procede de fabrication
WO2012158151A1 (fr) * 2011-05-13 2012-11-22 H2Oil Corporation Additif (de nanotechnologie) en microémulsion pour huile
JP6115702B2 (ja) * 2012-10-12 2017-04-26 裕子 森山 エンジンオイル用添加剤
US11041137B2 (en) * 2013-10-29 2021-06-22 Croda, Inc. Lubricant composition comprising hydroxycarboxylic acid derived friction modifier
EP3227411B1 (fr) 2014-12-03 2019-09-04 Drexel University Incorporation directe de gaz naturel dans des combustibles liquides hydrocarbonés

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GB800895A (en) * 1955-10-20 1958-09-03 Socony Mobil Oil Co Inc Marine diesel lubricant
GB827531A (en) * 1956-02-16 1960-02-03 Rech S Purfina S A Lab De Improvements in emulsion-type lubricants
US2975132A (en) * 1956-06-18 1961-03-14 California Research Corp Emulsifiable lubricant compositions
US2944023A (en) * 1957-01-15 1960-07-05 Socony Mobil Oil Co Inc Anticorrosive marine diesel lubricant
GB868893A (en) * 1957-11-15 1961-05-25 Taiyo Kako Kabushiki Kaisha Emulsified lubricating oil of water-in-oil type
US3281356A (en) * 1963-05-17 1966-10-25 Lubrizol Corp Thermally stable water-in-oil emulsions
US3342733A (en) * 1964-10-05 1967-09-19 Exxon Research Engineering Co Preparation of colloidal carbonates in hydrocarbon media
US3981813A (en) * 1975-05-12 1976-09-21 Standard Oil Company (Indiana) Hydraulic fluid
EP0584711A1 (fr) * 1992-08-22 1994-03-02 Hoechst Aktiengesellschaft Dérivés d'acide alkényl succinique comme agent auxiliaire du travail des métaux

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014033634A3 (fr) * 2012-08-29 2014-04-17 Indian Oil Corporation Limited Additif de lubrifiant et compositions d'huile de lubrifiant et leur procédé de préparation
EP3495462A1 (fr) * 2017-12-11 2019-06-12 Infineum International Limited Compositions neutralisant les acides à faible teneur en cendres et sans cendres et compositions d'huile lubrifiante les contenant

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EP1404786A1 (fr) 2004-04-07
JP2004531638A (ja) 2004-10-14
US20040248747A1 (en) 2004-12-09

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