Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
  • C10L1/303—Organic compounds compounds not mentioned before (complexes) derived from metals boron compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
• • 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
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
  • C10M2227/061—Esters derived from boron
• • 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
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
  • C10M2227/061—Esters derived from boron
  • C10M2227/062—Cyclic esters
• • 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
  • C10N2050/10—Semi-solids; greasy

Definitions

• the invention relates to lubricant and liquid fuel compositions.
• it relates to the use of borated derivatives of hydrocarbyl vicinal diols in liquid fuels and lubricants to reduce friction and fuel consumption in internal combustion engines.
• liquid fuel or lubricant composition comprising a major amount of fuel or lubricant and a friction-reducing or anti-oxidant amount of a borated hydrocarbyl vicinal diol containing from 10 to 30 carbon atoms.
• Alcohols are well known for their lubricity properties when formulated into lubricating oils and for their water-scavenging , characteristics when blended into fuels.
• the use of vicinal hydroxyl-containing alkyl carboxylates such as glycerol monooleate have also found widespread use as lubricity additives.
• U.S. 2,788,326 discloses some of the esters suitable for the present invention, e.g. glycerol monooleate, as minor components of lubricating oil compositions.
• U.S. 3,235,498 discloses, among others, the same ester as just mentioned, as an additive to other oils.
• U.S. 2,443,578 teaches esters wherein the free hydroxyl is found in the acid portion, as for example in tartaric acid.
• borated hydrocarbyl vicinal diols As a fuel or lubricant additive. It is known that borated hydrocarbyl and borated aliphatic diols are known for other uses.
• U.S. 3,740,358 teaches a phenol-aldehyde foamable composition containing a boron compound, e.g. a material formed by reacting boric acid or boric oxide with such aliphatic hydroxyl-containing compound.
• alkyl terminal vicinal diol borate esters possess much improved solubility characteristics, especially in synthetic fluids, over those of the non-borated derivatives.
• These borates are non-corrosive to copper, possess anti-oxidant and potential anti-fatigue characteristics.
• the compositions also have significantly greater frictionreducing properties, higher viscosity indices and good low temperature characteristics and solubility characteristics when used in low additive concentrations than do other known additives.
• hydrocarbyl vicinal diols contemplated for use in this invention are hydrocarbyl diols having vicinal hydroxyls. They have the formula: R(-O H ) 2 wherein R is a hydrocarbyl group containing 10 to 30 carbon atoms.
• hydrocarbyl includes, but is not limited to decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl and the like.
• R can be linear or branched, saturated or unsaturated with linear saturated members being preferred to maximize friction reduction.
• the two hydroxyl groups can be anywhere along the hydrocarbyl chain as long as they are on adjacent carbon atoms (vicinal), but the terminal diols are much preferred.
• the vicinal diols can be synthesized using several methods known to the art such as that described in J. Am. Chem. Soc., 68, 1504 (1946) which involves the hydroxylation of 1-olefins with peracids. Vicinal diols can also be prepared by the peroxytrifluoroacetic acid method for the hydroxylation of olefins as described in J. Am. Chem. Soc., 76, 3472 (1954). Similar procedures can be found in U.S. 2,411,762, U.S. 2,457,329, U.S. 2,455,892.
• the diols can also be prepared via catalytic epoxidation of an appropriate olefin followed by hydrolysis to form the appropriate vicinal diol.
• the preferred borated vicinal diols contain 12 to 20 carbon atoms. Below a carbon number of 12, friction-reducing properties as significantly reduced. Above a carbon number of 20, solubility constraints become significant. Preferred are the C 14 - C 17 hydrocarbyl groups in which solubility, frictional characteristics and other properties are maximized.
• diols contemplated for reaction with the boron compound are 1,2-hexanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1,2-pentadecanediol, 1,2-octadecanediol, 1,2-mixed C 15 -C 18 -alkanediols and mixtures thereof.
• the boronated compound used in this invention can be made using a single diol or two or more diols.
• a mixture of diols can contain from about 5% to about 95% by weight of any one diol, the other diol or diols being selected such that it or they together comprise from about 95% to about 5% by weight of the mixture. Such mixtures are often preferred to the single diol.
• Reaction with the boron compound of the formula (RO) x B(OH)y where R is a C 1 to C 6 alkyl, x is 0 to 3 and y is 0 to 3, the sum of x and y being 3, can be performed in the presence of an alcoholic solvent, such as butanol or pentanol, or a hydrocarbon solvent such as benzene, toluene or xylene, or mixtures of such solvents.
• Reaction temperatures of 90°C to 260 0 C or more can be used, but 110 to 200°C is preferred. Reaction times can be 1 to 24 hours and more.
• a stoichiometric amount of boric acid can be used, or an excess thereof can be used to produce a derivative containing from about 0.1% to about 10% of boron. At least 5 to 10% of the available hydroxyl groups of the diol should be borated to derive substantial beneficial effect. Conversely, a stoichiometric excess of boric acid (more than an equivalent amount of boronating agent compared to diol hydroxyl groups) can also be charged to the reaction medium resulting in a product containing the stated amount of boron.
• the boronated diols can also be borated with a trialkyl borate such as tributyl borate, often in the presence of boric acid. Preferred reaction temperatures for boration with the borate will range from 180°C to 280°C. Times can be from 2 to 12 hours, or more.
• the borated esters are used with lubricating oils to the extent of from 0.1% to 10% by weight of the total composition.
• other additives such as detergents, anti-oxidants, anti-wear agents may be present. These can include phenates, sulfonates, succinimides, zinc dithiophosphates, polymers, calcium and magnesium salts.
• the lubricants contemplated for use with the esters herein disclosed include mineral and synthetic hydrocarbon oils of lubricating viscosity mixtures of mineral oils and synthetic oils and greases from any of these, including mixtures.
• the synthetic hydrocarbon oils include long-chain alkanes such as cetanes and olefin polymers such as oligomers of hexane, octene, decene, and dodecene, etc. These vicinal diols are especially effective in synthetic oils formulated using mixtures of synthetic hydrocarbon olefin oligomers and lesser amounts of hydrocarbyl carboxylate ester fluids.
• the other synthetic oils which can be used alone with the borated compounds of this invention, or which can be mixed with a mineral or synthetic hydrocarbon oil, include (1) fully esterified ester oils, with no free hydroxyls, such as pentaerythritol esters of monocarboxylic acids having 2 to 20 carbon atoms, trimethylolpropane esters of monocarboxylic acids having 2 to 20 carbon atoms, (2) polyacetals and (3) siloxane fluids.
• Especially useful among the synthetic esters are those made from polycarboxylic acids and monohydric alcohols.
• ester fluids made by fully esterifying pentaerythritol, or mixtures thereof with di- and tripentaerythritol, with an aliphatic monocarboxylic acid containing from 1 to 20 carbon atoms, or mixtures of such acids.
• thickening agents can be used in the greases of this invention. Included among the thickening agents are alkali and alkaline earth metal soaps of fatty acids and fatty materials having from 12 to 30 carbon atoms per molecule.
• the metals are typified by sodium, lithium, calcium and barium.
• Fatty materials are illustrated by stearic acid, hydroxystearic acid, stearin, cottonseed oil acids, oleic acid, palmitic acid, myristic acid and hydrogenated fish oils.
• thickening agents include salt and salt-soap complexes as calcium stearate-acetate (U.S. Patent No. 2,197,263), barium stearate acetate (U.S. Patent No. 2,564,561), calcium stearate-caprylateacetate complexes (U.S. Patent No. 2,999,065), calcium caprylate-acetate (U.S. Patent No. 2,999,066), and calcium salts and soaps of low-, intermediate- and high-molecular weight acids and of nut oil acids.
• salt and salt-soap complexes as calcium stearate-acetate (U.S. Patent No. 2,197,263), barium stearate acetate (U.S. Patent No. 2,564,561), calcium stearate-caprylateacetate complexes (U.S. Patent No. 2,999,065), calcium caprylate-acetate (U.S. Patent No. 2,999,066), and calcium salts and soaps of low
• Another group of thickening agents comprises substituted ureas, phthalocyanines, indanthrene, pigments such as perylimides, pyromellitdiimides, and ammeline.
• the preferred thickening gelling agents employed in the grease compositions are essentially hydrophobic clays.
• Such thickening agents can be prepared from clays which are initially hydrophilic in character, but which have been converted into a hydrophobic condition by the introduction of long chain hydrocarbon radicals into the surface of the clay particles; prior to their use as a component of a grease composition, as, for example, by being subjected to a preliminary treatment with an organic cationic surface active agent, such as an onium compound.
• Typical onium compounds are tetraalkylammonium chlorides, such as dimethyl dioctadecyl ammonium chloride, dimethyl dibenzyl ammonium chloride and mixtures thereof.
• the clays which are useful as starting materials in forming the thickening agents to be employed in the grease compositions can comprise the naturally occurring chemically unmodified clays.
• These clays are crystalline complex silicates, the exact composition of which is not subject to precise description, since they vary widely from one natural source to another.
• These clays can be described as complex inorganic silicates such as aluminum silicates, magnesium silicates, barium silicates, and the like, containing, in addition to the silicate lattice, varying amounts of cation-exchangeable groups such as sodium.
• Hydrophilic clays which are particularly useful for conversion to desired thickening agents include montmorillonite clays, such as bentonite, attapulgite, hectorite, illite, saponite, sepiolite, biotite, vermiculite, zeolite clays, and the like.
• the thickening agent is employed in an amount from 0.5 to 30, and preferably from 3 percent to 15, percent by weight of the total grease composition.
• liquid fuels contemplated include liquid hydrocarbon fuels such as fuel oils, diesel oils and gasolines and alcohol fuels such as methanol and ethanol or mixtures of these fuels.
• Solvents that can be used include the hydrocarbon solvents, such as toluene, benzene, xylene, and the like, alcohol solvents such as propanol, butanol, pentanol and the like, as well as mixtures of hydrocarbon solvents or alcohol solvents and mixtures of hydrocarbon and alcohol solvents.
• hydrocarbon solvents such as toluene, benzene, xylene, and the like
• alcohol solvents such as propanol, butanol, pentanol and the like, as well as mixtures of hydrocarbon solvents or alcohol solvents and mixtures of hydrocarbon and alcohol solvents.
• the product of the Examples were blended into a fully formulated 5W-20 synthetic automotive engine oil containing other additives, such as detergent, dispersant, anti-oxidant and the like additives and evaluated using the Low Velocity Friction Apparatus (LVFA) test.
• LVFA Low Velocity Friction Apparatus
• the compounds were evaluated as friction modifiers in accordance with the following test.
• the Low Velocity Friction Apparatus is used to measure the friction of test lubricants under various loads, temperatures, and sliding speeds.
• the LVFA consists of a flat SAE 1020 steel surface (diam. 3.8 cm.) which is attached to a drive shaft and rotated over a stationary, raised, narrow ringed SAE 1020 steel surface of 51.6 mm 2 (area 0.08 in. 2 ). Both surfaces are submerged in the test lubricant. Friction between the steel surfaces is measured as a function of the sliding speed at a lubricant temperature of 121°C. The friction between the rubbing surfaces is measured using a torque arm-strain gauge system.
• the strain gauge output which is calibrated to be equal to the coefficient of friction, is fed to the Y axis of an X-Y plotter.
• the speed signal from the tachometer-generator is fed to the X-axis.
• the piston is supported by an air bearing.
• the normal force loading the rubbing surfaces is regulated by air pressure on the bottom of the piston.
• the drive system consists of an infinitely variable-speed hydraulic transmission driven by a 373W (1/2 HP) electric motor. To vary the sliding speed, the output speed of the transmission is regulated by a lever-cam motor arrangement.
• test lubricant The rubbing surfaces and 12-13 ml of test lubricant are placed on the LVFA. A 1756 kPa (240 psig) load is applied, and the sliding speed is maintained at 12.2 m/s (40 fpm) at ambient temperature for a few minutes. A plot of coefficients of friction (U k ) over the range of sliding speeds, 1.5 to 12.2 m/s (5 to 40 fpm, 25-195 rpm), is obtained. A minimum of three measurements is obtained for each test lubricant. Then, the test lubricant and specimens are heated to 121°C, another set of measurements is obtained, and the system is run for 50 minutes at 121°C, 240 psi and 12.2 m/s (40 fpm) sliding speed.
• U k coefficients of friction
• the data obtained are shown in Table 1.
• the data in Table 1 are reported as percent reduction in coefficient of friction at two speeds.
• the frictionreducing ester additives were evaluated in a fully formulated 5W-20 synthetic lubricating oil comprising an additive package including anti-oxidant, detergent and dispersant.
• the oil had the following general characteristics:
• the products of this invention were tested in a catalytic oxidation test for lubricants, using as the base oil a 200" solvent paraffinic neutral mineral oil.
• the test lubricant composition is subjected to a stream of air bubbled through the composition at a rate of 5 liters per hour at 163°C for 40 hours.
• Present in the composition are metals commonly used as materials of engine construction, namely:
• Inhibitors for oil are rated on the basis of prevention of oil deterioration as measured by the increase in acid formation or neutralization number (NN) and kinematic viscosity (KV) occasioned by the oxidation. The results of the tests are reported in Table 2.

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Citations (4)

• 1982
  • 1982-08-17 NZ NZ201613A patent/NZ201613A/xx unknown
  • 1982-08-17 ZA ZA825972A patent/ZA825972B/xx unknown
  • 1982-08-24 CA CA000410016A patent/CA1198726A/en not_active Expired
  • 1982-09-03 AU AU88016/82A patent/AU553247B2/en not_active Ceased
  • 1982-09-21 DE DE8282304950T patent/DE3276869D1/de not_active Expired
  • 1982-09-21 BR BR8205535A patent/BR8205535A/pt unknown
  • 1982-09-21 AT AT82304950T patent/ATE28661T1/de not_active IP Right Cessation
  • 1982-09-21 JP JP57164817A patent/JPS5865792A/ja active Granted
  • 1982-09-21 EP EP82304950A patent/EP0075478B1/de not_active Expired

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