WO2015140822A1 - Liquides ioniques exempts d'halogène comme lubrifiant ou comme additifs de lubrifiant et procédé pour leur préparation - Google Patents

Liquides ioniques exempts d'halogène comme lubrifiant ou comme additifs de lubrifiant et procédé pour leur préparation Download PDF

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WO2015140822A1
WO2015140822A1 PCT/IN2015/050022 IN2015050022W WO2015140822A1 WO 2015140822 A1 WO2015140822 A1 WO 2015140822A1 IN 2015050022 W IN2015050022 W IN 2015050022W WO 2015140822 A1 WO2015140822 A1 WO 2015140822A1
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lubricant
ionic liquids
group
alkyl
oils
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PCT/IN2015/050022
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Om Prakash KHATRI
Rashi GUSAIN
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Council Of Scientific & Industrial Research
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Priority to US15/126,963 priority Critical patent/US20170096614A1/en
Priority to EP15722777.8A priority patent/EP3119859A1/fr
Publication of WO2015140822A1 publication Critical patent/WO2015140822A1/fr

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    • 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
    • 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
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/40—Lubricating compositions characterised by the base-material being a macromolecular compound containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/1213—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/1253—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/077—Ionic Liquids
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure

Definitions

  • the present invention relates to halogen free ionic liquids based lubricant or lubricant additives and a process for the preparation thereof.
  • the present invention provides lubricant or lubricant additives composed of halogen-, phosphorus, and sulphur-free ionic liquids containing fatty acid anions. More particularly, the invention relates to the reduction of friction and wears using these ionic liquids as lubricants or lubricant additives mixed with mineral, synthetic, native lube oils.
  • the good lubricant should be able to (a) keep surfaces of working parts separate under all loads, temperatures and speed, thus reducing the friction and wear, (b) enhance the energy efficiency of the system, (c) dissipate the heat from the contact surfaces and (d) increase the life of sliding machine tools by- protecting their contact surfaces.
  • Ionic liquids are poorly coordinated salts, composed of bulk organic cations and organic / inorganic anions, which exist in liquid phase at below 100 °C.
  • ionic liquids have attracted significant attention for diversified range of applications owing to combination of their unique and tunable physico-chemical characteristics such as low vapor pressure, good thermal stability, non-flammability, excellent conductivity, high viscosity, favorable miscibility for organic and inorganic compounds etc.
  • These features make ionic liquids as potential candidates for lubricant applications to reduce both friction and wear.
  • High conductivity of ionic liquids dissipate the heat from contact surfaces, which reduced the material loss from contact surfaces.
  • Most of ionic liquids are non-flammable, hence they are more safer in transport and storage perspective compared to the conventional lube oils. Many ionic liquids are non-volatile hence make a significant positive environmental impact.
  • a lubrication oil composition comprises a major amount of a base oil and a minor amount of an additive which is a non-halide, non-aromatic ionic liquids with a general formula of C A . where cation C being a quaternary phosphonium or ammonium ion, and the anion A-. comprising at least one oxygen atom and having an ionic head group attached to at least one alkyl or alicyclic hydrocarbyl group.
  • the ionic liquid may be used as anti-wear and a friction modifier in the lubricating oil composition.
  • the lubricating oil composition may be used in an ignition engine.
  • the addressed ionic liquids contains phosphorus and sulphur elements as main constituents, which are not only hazardous and toxic to environment, but also corrodes the engineering surfaces of metals.
  • an invention relates to the use of ionic liquids for improving the lubricating effect of synthetic, mineral and native oils, in particular to an improved lubricating composition that is protected from thermal and oxidative attack.
  • the ionic liquids addressed in this invention carries halogen, phosphorus and sulphur elements as main constituents which are not only hazardous and toxic to environment, but also corrodes the engineering surfaces of metals.
  • the main object of the present invention is to provide halogen-free ionic liquids based lubricant or lubricant additives and a process for the preparation thereof.
  • Another object of the present invention is to provide lubricants or lubricant additives composed of halogen-, phosphorus- and sulphur-free ionic liquids containing fatty acids anions, which exhibit superior friction-reducing, anti-wear propeities.
  • Another object of the present invention is to provide halogen-, phosphorus- and sulphur-free ionic liquids as lubricant or lubricant additive, which minimize hazardous and corrosion effect to the environment and engineering surfaces.
  • Still another object of the present invention is to provide ionic liquids that exhibits a better combination of friction, wear and heat transfer properties as compared with corresponding lubricant or lubricant additives.
  • the present invention provides a lubricant or lubricant additive(s) composition
  • a lubricant or lubricant additive(s) composition comprising an ionic liquid(s), wherein anions in the ionic liquid(s) are fatty acids of the general formula RCOO-, wherein R is selected from C4 to C30 straight chain alkyl, branched alkyl, straight or branched alkenyl, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl; alkyl or alkenyl group(s) containing heteroatom selected from -OH, -CN, -C-0-C-; and cations in the ionic liquids are selected from the group consisting of:
  • Rl to R12 is similar or different from one another, selected from the group consisting of hydrogen, -OH, C I to C I 8 alkyl group(s) including straight chain or branched structures.
  • the ionic liquids are substantially or completely free of halogen, phosphorous, and/or sulphur.
  • ionic liquid are selected from Tetrabutyiammonium oleate (TBA-OL), 1-Hexyl— metliylimidazolium oleate (HMIM-OL) and Tetrabutyiammonium linoleate (TBA-LN), Tetrabutyiammonium caprylate, Tetrabutyiammonium caprate, Tetrabutyiammonium laurate, Tetrabutyiammonium myrisate, Hexyldimethylcyclohexyl ammonium oleate and Dioctylmethylpentylammonium oleate.
  • the composition further comprising one or more additives selected from dispersants, corrosion inhibitors, detergents, antioxidants, anti-wear and extreme pressure additives, viscosity improvers, fiction improvers, oiliness improver, metal deactivator, demulsiiiers, pour point depressants, foam inhibitors, seal-swelling agents, antimicrobial.
  • the lubricant or lubricant additive composition is having high friction reducing and anti-wearing properties.
  • a lubricating oil comprising the lubricant additive composition and a base lubricating oil.
  • the concentration of ionic liquid (s) as lubricant additive(s) in the base lubricant oil(s) is in the range of 0.5 to 10 wt %.
  • the base lubricant oil(s) is selected from synthetic, minerals and native base stock (s) or base oil (s).
  • the synthetic oils is selected from the group consisting of polymerized and interpolymerized olefins: polyalphaolefm (PAO) derived from olefins, dioi or triol or polyo!
  • PAO polyalphaolefm
  • mineral base oil (s) is selected from Group 1 (solvent refined mineral oils), Group II (hydrocracked mineral oils), Group III (severely hydrocracked oils, also referred to as synthetic or semi-synthetic oils), Group V (esters, napthenes, and others); native oil(s) as lube base stock (s) is selected from animal and vegetable oils, which are predominantly composed of triglycerides with minor components of mono- and diglycerides.
  • step (b) extracting the organic layer as obtained in step (a) using dichloromethane followed by washing with water then removing dichloromethane under reduced pressure subsequently drying under reduced pressure to get lubricant or lubricant additive composed of ionic liquid.
  • ionic liquids are salts of one or mixtures of fatty acids anions.
  • the suitable cations for the present invention may be imidazolium, ammonium, peridinium, pyrolidinium, pyrrolidinium and the like.
  • the contact surfaces are independently composed of metal, ceramic or alloys and more: including the thin film (s) of metallic or ceramic materials on the contact surfaces.
  • Figure 1 represents a bar graph of the friction coefficient for three representative fatty acid ionic liquids and two conventional lube oils.
  • Figure 2 represents a bar graph of the wear scar diameter (WSD) for three representative fatty acid ionic liquids and two conventional lube oils.
  • Figure 3 represents a composite bar graph of (a) wear scar diameter and (b) friction coefficient of tetrabutylammonium oleate with function of their concentration (wt %) blended with polyol ester lube base.
  • Ionic liquids are composed of ions (cations and anions) that are liquids at below 100 °C. Ionic liquids exhibit unique physico-chemical characteristics such as higher thermo-oxidative stability, negligible volatility, broad liquid range, non-flammability and excellent heat conductivity, which meet the requirements of high performance lubricants.
  • the flexible molecular structure with diversified range of cations and anions makes ionic liquids as versatile lubricants or lubricant additives for different engineering surfaces.
  • the inherent polarity of ionic liquids found to provide strong adsorption to the matting surfaces and forms thin film of low shearing strength, consequently, reduction in friction and wear.
  • the present invention provides halogen-, phosphorus- and sulphur-free ionic liquids composed of diversified cations and fatty acid anions as lube oils for anti-wear and anti -friction performance.
  • the lube oil can be comprised of a base oil and an ionic liquid or mixed of two or more ionic liquids formed of a cation and an anion and having an ion concentration of 0.5 wt % or more.
  • fatty acids in the form of ionic liquids as anions with various types of cations have been developed as anti-wear and friction-reducing agent. Owing to inherent polar nature of these fatty acids anions, they prone to interact with metallic surfaces and forms thin film of low shear strength, which reduces both friction and wear more efficiently compared to that of free fatty acids and fatty acids esters.
  • a preferred group of lube oil or lube base stock to which the ionic liquids can be added, use in the present invention may be consist of one or more base stock (s) or base oil (s) selected from synthetic, minerals and native base stock (s) or base oil (s). Natural and synthetic oils (or mixture thereof) can be used unrefined, refined or re-refined.
  • the synthetic oils may be selected from polymerized and interpolymerized olefins including commonly used polyalphaolefin (PAO) derived from olefins.
  • PAO polyalphaolefin
  • the synthetic oil may be selected from a diol or triol or polyol esters or polypheny! ether or alkylated di- or triphenyl ether, alkylated naphthalenes, alkylated benzene, polyglycols, polyalkylglycols, silicon oils, perfluoropolyethers and so on.
  • Mineral and synthetic lube base oil (s) or lube base stock (s) may be selected from Group I (solvent refined mineral oils).
  • Group II hydrocracked mineral oils
  • Group III severely hydrocracked oils, also referred to as synthetic or semi-synthetic oils
  • Group V esters, napthenes, and others.
  • oils Animal and vegetable oils (native oils) are predominantly composed of triglycerides with minor components of mono- and digh ccrides and other substances. These oils either as it is or in refined or chemically derived form by known methods such as trans-esterifi cations, hydrogenations, estolide formation and so on, may be selected to which ionic liquids can be added.
  • the use of native oils based on renewable raw materials is important owing to their advantages with regard to biodegradability and reducing or preventing C0 2 emission.
  • ionic liquid(s) added lubricants or ionic liquids as lubricants may contain one or more chemicals to provide other desired chemical and physical properties to the lubricating system.
  • chemical additives includes dispersants, corrosion inhibitors, detergents, antioxidants, anti-wear and extreme pressure additives, viscosity improvers, friction improvers, oiliness improver, metal deactivator, demulsifiers, pour point depressants, foam inhibitors, seal-swelling agents, antimicrobial additives etc.
  • aforementioned chemical additives are used in the ionic liquid(s) added lubricant in required quantity, to improve the performance characteristics and properties of the base oil(s) or base stock(s).
  • halogen-, phosphorus- and sulphur-free ionic liquids are salts of one or mixtures of fatty acids anions.
  • the general chemical structure of fatty acid (carboxylate) anion for the resent invention may be represented as formula I:
  • R may be C 4 to C 30 straight chain alkyl, branched alkyl, alkenyl (one or more double bonds) includes with or without branched structure, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl and so on.
  • the alkyl or alkenyl group(s) may contain heteroatom comprise groups such as -OH. - N.-C-O- - and so on.
  • R 1 to R 12 may be the similar or different from one another, represents a group consisting of hydrogen, -OH, C ( to C i8 alkyl group(s) includes straight chain or branched structure, C 2 to C !2 alkenyl group(s) includes straight chain or branched structure wherein the alkyl or alkenyl group(s) may contain heteroatom, C- to C 12 arylalkyl group(s), C7 to C 12 alkylaryl group(s).
  • the halogen-, phosphorus- and sulphur-free ionic liquids addressed in the present invention not only significantly reduces both friction coefficient and wear between two or more contact surfaces but also minimize the hazardous and corrosive effects.
  • the addressed halogen-, phosphorus- and sulphur-free ionic liquids in the present invention meets all these objectives and has an emergent scope for their practical utilization in lubrication applications.
  • TBA-OL ionic liquid may be represented by general formula III.
  • TBA-OL was prepared by mixing sodium salt of oleic acid (0.05 mol) in an aqueous solution of tetrabutylammonium bromide (0.05 mol ) at 45 °C for 4 hours under continuous stirring. This led to the formation of an organic layer in the reaction product, which was extracted using dichloromethane. This was followed by washing of organic content composed of TBA-OL ionic liquid with pure water until no more bromide ions were detected in the water. Finally, dichloromethane was removed under reduced pressure and the extracted product was dried in a vacuum oven at 80°C under reduced pressure for 48 hours. The synthesized ionic liquid was characterized by ⁇ MR and FTl R spectroscopy. The characterization detail is as follow
  • HM I M-OL ionic liquid may be represented by general formula IV.
  • H I -OL was prepared by mixing an cqui molar quantity of sodium salt of oleic acid (0.05 mol) and l-hexyl-3- methyiimidazoiium bromide (0.05 mol) at 45 °C for 4 hours under continuous stirring.
  • the prepared HMIM-OL ionic liquid was extracted using dichloromethane and washed with pure water for couple of times to remove the inorganic slat, until no more of bromide ions were detected in the water.
  • Hexyl-3-methylimidzolium bromide an ionic liquid precursor was prepared by using an equimolar amount of 1-bromohexane (0.1 mol) and N-methylimidazole (0.1 mol) in a round bottom flask. The reaction mixture was heated at 75 °C for 36 hours under a nitrogen atmosphere with continuous
  • TBA-L ionic liquid may be represented by general formula V.
  • TBA-LN was prepared by mixing sodium salt of linoleic acid (0.05 mol) in an aqueous solution of tetrabutylammonium bromide (0.05 mo! ) at 45 °C for 4 hours under continuous stirring. This led to the formation of an organic layer in the reaction product, which was extracted using dichloromethane. This was followed by washing of organic content composed of TBA-LN ionic liquid with pure water until no more bromide ions were detected in the water. Finally, dichloromethane was removed under reduced pressure and the extracted product was dried in a vacuum oven at 80°C under reduced pressure for 48 hours.
  • the synthesized ionic liquid was characterized by ⁇ NMR and FTIR spectroscopy. The characterization detail is as follows:
  • Lubricating properties in terms of friction coefficient and wear scar diameter (hereon it will be known as WSD) for the fatty acid ionic liquids as lubricants were evaluated on a four-ball test machine as per the ASTM D4172 standard test method.
  • two conventional lube oils (fully formulated 10W40 lube oil and pentaeiythritol tetraoleate, polyol ester) were also evaluated under similar test conditions.
  • a 12.7 mm steel ball under the 392 N load is rotated (rotating speed: 1200 rpm) against three stationary steel balls clamped in the holder at temperature of 75 °C for a test duration of 60 minutes.
  • the thin film of ionic liquids on metal surfaces avoid the direct contact between steel balls, consequently significant reduction in material loss ( SD) as shown in Figure 2. It is noted that all these ionic liquids performed better than 10W40 oil and polyol ester lube base stock.
  • variable concentrations (wt %) of fatty acid ionic liquid are mixed with the conventional polyol ester (pentaerythritol tetraoleate) lube base and then evaluated their friction coefficient and WSD on a four-ball test machine as per the ASTM D4172 standard test method.
  • TBA-OL was selected as representative fatty acid ionic liquid for this study.
  • the friction coefficient and WSD for polyol ester lube oil are found to be about 0.08 and 556 ⁇ . respective! ⁇ '. Both friction coefficient and WSD decreases significantly with increasing concentration of tetrabutylammonium oleate.
  • the 2 wt% of tetrabutylammonium oleate in polyol ester lube base shows 56% and 22% reduction in friction coefficient and WSD, respectively, compared to that of polyol ester lube base.
  • Lubricant with high viscosity can bear high contact pressure between moving surfaces, however, it's high internal friction provides larger resistance to the movement of the lubricating parts.
  • a lubricant with low viscosity offers low resistance to shear but the lubricant can be squeezed out of the lubricating surfaces, that may lead to high friction and more energy loss.
  • viscosities and viscosity index of 1.5 wt% fatty acids ionic liquids blended with polyol ester lube base stock are evaluated and shown in Table 1. There is no significant change in both kinematic viscosities at 40 and 100 °C, and viscosity index of polyol ester on blending of fatty acid ionic liquids. High viscosity index reveals that all blends of various fatty acid ionic liquids can be even used at high temperature and are suitable for lubrication applications.
  • Table 1 Kinematic viscosity and viscosity index of polyol ester having 1.5 % various fatty acids ionic liquids.
  • Lubrication properties in terms of friction coefficient and WSD for 1.5 wt% fatty acid ionic liquids as lubricants additive blended with polyol ester lube base were evaluated on a four-ball test machine as per the ASTM D4172 standard test metliod.
  • conventional polyol ester lube base was also evaluated under similar test conditions.
  • a 12.7 mm steel ball under the 392 N load is rotated (rotating speed: 1200 rpm ) against three stationary steel balls clamped in the holder at temperature of 75 °C for a test duration of 60 minutes.
  • the four balls were fully flooded with a test lube sample, which was used for the friction and WSD evaluation.
  • the friction force was measured during the tri bo-test and WSD on the lubricated steel balls was examined by the microscopic measurements.
  • the friction coefficient and SD for representative fatty acid ionic liquids and polyol lube base are compared in Table 2. All fatty acid ionic liquids as additives having wide structural variations shows better lubricating properties by reducing both friction coefficient (upto 54%) and WSD (upto 30%) compared to that of for polyol ester lube base. This is attributed to the formation of tribo thin film on contact surfaces, which provides low resistance to shear and avoid the direct contact between the metallic surfaces, resulting in significant reduction in both friction coefficient and WSD.
  • Table 2 WSD and friction coefficient of representative fatty acids ionic liquids blended ( 1.5 wt%) with polyol ester.
  • All fatty acid ionic liquids as additives shows very good lubricating properties by reducing both friction coefficient (17 - 29%) and wear scar diameter (upto 37%) compared to that for 10W40 lube oil.
  • the fully formulated 10W T 40 lube oil contains all required additives including friction improver and anti-wear additives, but still 1 wt% dose of these fatty acids ionic liquids in such fully formulated oil, shows significantly improved tribo-characteristics. This is attributed to the formation of tribo thin film of low shearing strength on the contact surfaces.
  • the present invention on halogen-, phosphorus- and sulphur-free ionic liquids as lubricants or lubricant additives composed of fatty acids anions exhibit superior anti-wear and antifriction properties compared to the conventional lubricants.
  • the main advantages of the present invention are: o provide lubricants or lubricant additives composed of halogen-, phosphorus- and sulphur- free ionic liquids containing fatty acids anions, which exhibit superior friction-reducing and anti-wear properties.
  • o provide halogen-, phosphorus- and sulphur-free ionic liquids as lubricant or lubricant additive, which minimize hazardous and corrosion effect to the environment and engineering surfaces, respectively.
  • o provide halogen-, phosphorus- and sulphur-free ionic liquids that exhibits a better combination of friction, wear and heat transfer properties as compared with corresponding lubricant or lubricant additives.

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

Abstract

L'invention concerne un lubrifiant ou un additif de lubrifiant, composé de liquides ioniques exempts d'halogène, de phosphore et de soufre, contenant des anions d'acide gras, présentant des propriétés supérieures de réduction de friction et anti-usure. De préférence, la composition lubrifiante comprend une huile de base et un liquide ionique ou un mélange de deux liquides ioniques ou plus, présentant une concentration de 0,5 % en poids ou plus. Ces liquides ioniques exempts d'halogène, de phosphore et de soufre comme lubrifiant ou additif de lubrifiant présentent un effet de risque et corrosif minimums respectivement sur l'environnement et sur les surfaces d'ingénierie. La formule chimique générale d'un anion d'acide gras est représentée comme RCOO- ; attendu que R peut représenter alkyle à chaîne droite, alkyle ramifié, cycloalkyle, cycloalkyle substitué par alkyle, alkyle substitué par cycloalkyle, alcényle (une seule ou plusieurs doubles liaisons) en C4 à C30, avec ou sans structure ramifiée et peut contenir un hétéroatome.
PCT/IN2015/050022 2014-03-18 2015-03-17 Liquides ioniques exempts d'halogène comme lubrifiant ou comme additifs de lubrifiant et procédé pour leur préparation WO2015140822A1 (fr)

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US15/126,963 US20170096614A1 (en) 2014-03-18 2015-03-17 Halogen free ionic liquids as lubricant or lubricant additives and a process for the preparation thereof
EP15722777.8A EP3119859A1 (fr) 2014-03-18 2015-03-17 Liquides ioniques exempts d'halogène comme lubrifiant ou comme additifs de lubrifiant et procédé pour leur préparation

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CN117210265A (zh) * 2023-08-04 2023-12-12 上海应用技术大学 一种石墨复合材料润滑油及其制备方法
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WO2023249481A1 (fr) * 2022-06-21 2023-12-28 Petroliam Nasional Berhad (Petronas) Liquide ionique sans cendre

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CN105254667A (zh) * 2015-11-17 2016-01-20 中国科学院兰州化学物理研究所 功能化油溶性离子液体及其制备方法和应用
CN105646239A (zh) * 2016-01-12 2016-06-08 宝鸡文理学院 一种无氟烷基羧酸离子液体及其制备方法和应用
US10752856B2 (en) 2017-05-24 2020-08-25 Ingevity South Carolina, Llc Fatty acid and rosin based ionic liquids
CN109485573A (zh) * 2018-11-23 2019-03-19 宝鸡文理学院 一种芳香族二羧酸离子液体及其制备方法和应用
CN109485573B (zh) * 2018-11-23 2021-04-30 宝鸡文理学院 一种芳香族二羧酸离子液体及其制备方法和应用
CN109400883A (zh) * 2018-11-29 2019-03-01 中国科学院兰州化学物理研究所 一种抗空间辐照poss基原位离子液体及其制备方法和应用
CN109400883B (zh) * 2018-11-29 2021-03-30 中国科学院兰州化学物理研究所 一种抗空间辐照poss基原位离子液体及其制备方法和应用
CN113493719B (zh) * 2020-04-07 2022-06-03 中国石油天然气股份有限公司 一种燃气轮机润滑油组合物
CN113493719A (zh) * 2020-04-07 2021-10-12 中国石油天然气股份有限公司 一种燃气轮机润滑油组合物
WO2021209296A1 (fr) * 2020-04-16 2021-10-21 Total Marketing Services Liquide ionique à base d'ammonium et son utilisation comme additif pour lubrifiant
CN115551975A (zh) * 2020-04-16 2022-12-30 道达尔能量联动技术公司 基于铵的离子液体及其作为润滑剂添加剂的用途
CN115551975B (zh) * 2020-04-16 2024-01-23 道达尔能量联动技术公司 基于铵的离子液体及其作为润滑剂添加剂的用途
US12065622B2 (en) 2020-04-16 2024-08-20 Totalenergies Onetech Ammonium-based ionic liquid and its use as a lubricant additive
CN114806686A (zh) * 2022-04-15 2022-07-29 西安交通大学 一种铝箔、铜箔用易挥发复合型切削液及其制备方法
WO2023249482A1 (fr) * 2022-06-21 2023-12-28 Petroliam Nasional Berhad (Petronas) Composition comprenant de l'huile de base et un liquide ionique sans cendre
WO2023249481A1 (fr) * 2022-06-21 2023-12-28 Petroliam Nasional Berhad (Petronas) Liquide ionique sans cendre
CN117210265A (zh) * 2023-08-04 2023-12-12 上海应用技术大学 一种石墨复合材料润滑油及其制备方法

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