JPH0328478B2 - - Google Patents

Abstract

Multifunctional additives are provided for fuel and lubricant compositions. The additives are borated hydrocarbyl vicinal diols, made by reacting the diol with a boron-containing compound such as boric acid or trialkyl borate.

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to lubricants and liquid fuel compositions. More particularly, the present invention relates to the use of borate derivatives of hydrocarbyl vicinal diols in liquid fuels and lubricants to reduce internal engine friction and fuel consumption. The present invention provides a primary amount of fuel or lubricant and a friction-reducing or oxidation-inhibiting amount of carbon atoms ranging from 10 to
A liquid fuel or lubricant comprising a borated hydrocarbyl vicinal diol containing 30% is provided. Alcohol is well known for its lubricating performance when blended into lubricating oil and its water-trapping properties when mixed into fuel. The use of vicinal hydroxyl-containing alkyl carboxylates, such as glycerol monooleate, is also known for widespread use as lubricating additives. U.S. Pat. No. 2,788,326 discloses certain esters suitable for the present invention, such as glycerol monoolefinate, as minor components of lubricating oil compositions. US Pat. No. 3,235,498 discloses the same esters described above as additives for other oils, among others. US Patent No.
No. 2,443,578 teaches esters in which a free hydroxyl is present in the acid moiety, using tartaric acid as an example. This patent, as well as a number of other patents, are directed to the use of esters as additives. U.S. Patent No. 2798083, U.S. Patent No. 2820014, U.S. Patent No. 3115519,
No. 3282971 and other patents such as No. 3309319 and R.R. Barnes (RR.
Barnes) et al., “Synthetic Ester Lubricants”,
Lubrication Engineering, August,
454-457 (1975) teaches lubricants made from polyhydric alcohols and acids that are hydroxyl-free except in association with acid functionality. To the best of our knowledge, no efforts have been made to use borate hydroxyl vicinal diols as fuel or lubricant additives. It is known that hydrocarbyl borates and aliphatic diols of borates have other known uses. For example, U.S. Pat. No. 3,740,358 teaches phenol-aldehyde foamable compositions containing boron compounds, such as materials produced by reacting boric acid or boron oxide with such aliphatic hydroxyl-containing compounds. It has now been discovered that boration of these long chain alkyl vicinal terminal diols significantly improves friction reducing properties and imparts an oxidation inhibitor component to these new compositions. In addition to the friction-reducing properties mentioned above, alkyl vicinal terminal diol borate esters have properties that greatly improve solubility, particularly in synthetic fluids, over non-borate derivative esters. These borates are non-corrosive to copper and have anti-oxidation properties and potential anti-fatigue properties. Additionally, the composition also has significantly greater friction reducing properties, a higher viscosity index, and better low temperature and solubility properties than other known additives when used at low additive concentrations. Hydrocarbyl vicinal diols contemplated for use in the present invention are hydrocarbyl diols having vicinal hydroxyl groups. They have the formula R(-OH) ₂ . where R is a hydrocarbyl group containing 10 to 30 carbon atoms. As used herein, "hydrocarbyl" includes, but is not limited to, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl, and the like. R is straight chain or branched, saturated or unsaturated, with straight chain saturated being preferred for maximum friction reduction. The two hydroxyl groups can be any hydrocarbyl chain as long as they are on adjacent carbon atoms, but terminal diols are highly preferred. J. Am. Chem, in which the vicinal diol includes hydroxylation of 1-olefin with peracid;
Soc., Journal of the American Chemical Society, Vol. 68, p. 1504 (1946). Neighboring diols are also J. Am. Chem, Soc., Vol. 76,
It can also be produced by the peroxytrifluoroacetic acid method of hydroxylating olefins as described on page 3472 (1954). A similar method is disclosed in U.S. Pat. No. 2,411,762;
It is also found in the same No. 2457329 and the same No. 2455892. The diol can also be prepared by epoxidation of the appropriate olefin followed by hydrolysis to form the appropriate vicinal diol. Preferably, the borate vicinal diol contains 12 to 20 carbon atoms. When the number of carbon atoms is 12 or less, the friction reduction property decreases significantly. When the number of carbon atoms is 20 or more, solubility becomes significantly restricted. _C14 - _C17 hydrocarbyl groups are preferred as solubility, tribological properties and other properties are maximally enhanced. Among the diols, those expected to react with boron compounds are 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1,
2-pentadecanediol, 1,2-octadecanediol, 1,2-mixed _C15 - _C18 -alkanediols and mixtures thereof. The borate compounds used in this invention can be prepared using one diol or more than one diol. The mixture of diols is approximately 5% by weight.
- about 95% by weight of any one diol and one or both of the other diols or diols - about 95% by weight of the mixture - about 5% by weight of the mixture;
Including weight percent. A single diol is often preferred for such mixtures. Formula (RO) _x B(OH) _y (wherein, R is a C ₁ -C ₆ alkyl group, x is 0-3,
y is 0-3 and the sum of x and y is 3) with a boron compound in the presence of an alcoholic solvent such as butanol or pentanol or a hydrocarbon solvent such as benzene, toluene, xylene, or a mixture of such solvents. To be carried out below. The reaction temperature is
Temperatures of 90°C to 260°C or higher are used, preferably 110 to 200°C. The reaction time is preferably 1 to 24 hours or more.
Up to stoichiometric amounts of boric acid may be used, or an excess thereof may be used to produce derivatives containing from about 0.1 to about 10% boron. At least 5 to 10% of the available hydroxyl diol should be borated in order to obtain a substantial beneficial effect. Conversely, a stoichiometric excess of boric acid (more than an equilibrium amount of boronating agent with respect to the hydroxyl groups of the diol) can also be added to the reaction medium, resulting in a product containing the aforementioned amount of boron. Borated diols are also often borated with trialkyl borates such as tributyl borate in the presence of boric acid. The preferred reaction temperature for boration with borate is in the range of 180°C to 280°C. The duration is 2 to 12 hours or more. As mentioned above, boric acid ester accounts for 0.1 to 10 of the total composition.
Used in lubricating oils in a range of % by weight. Additionally, other additives such as detergents, oxidation inhibitors, anti-wear agents can also be added. These include phenates, sulfonates, succinimides, zinc dithiophosphates, polymers, calcium and magnesium salts. Potential lubricants for use with the esters disclosed herein include mineral oils and synthetic hydrocarbon oils and mixtures thereof, including lubricating viscosity mixtures of mineral oils and synthetic petroleum oils and greases therefrom.
Synthetic hydrocarbon oils include long chain alkanes such as cetane and olefin polymers such as hexene, octene, decene, dodecene, and the like. These vicinal diols are particularly useful in synthetic petroleum oils formulated using mixtures of synthetic hydrocarbon olefin oligomers and smaller amounts of hydrocarbyl carboxylic acid ester liquids. Other synthetic oils in which the borate compounds of the present invention are used alone or mixed with mineral oils or synthetic hydrocarbon oils include (1) 2 carbon atoms;
fully esterified ester oils without free hydroxyl groups, such as pentaerythritol esters of monocarboxylic acids with ~20 carbon atoms, trimethylolpropane esters of monocarboxylic acids with 2 to 20 carbon atoms, (2) polyacetals and (3) Includes siloxane liquid. Particularly useful synthetic esters are those made from polycarboxylic acids and monohydric alcohols. Further preferred are ester solutions prepared by extensive esterification of pentaerythritol or di- and tripentaerythritol and mixtures thereof with aliphatic monocarboxylic acids containing from 1 to 20 carbon atoms or mixtures of such acids. . A wide variety of thickeners can be used in the greases of this invention. Thickeners include alkali metals and alkaline earth metals of fatty acids and fatty materials having from 12 to 30 carbon atoms in the molecule. Representative metals include sodium, lithium, calcium, and barium. Fat materials include stearic acid, hydroxystearic acid, stearin, cottonseed oil acid, olefinic acid,
Palmitic acid, myristic acid and hydrogenated fish oil are specific examples. Other thickening agents include salt and calcium stearate-acetate (U.S. Pat. No. 2,197,263), barium stearate acetate (U.S. Pat. No. 2,564,561),
Salts such as calcium stearate-caprylate acetate (U.S. Pat. No. 2,999,065) and calcium caprylate-acetate (U.S. Pat. No. 2,999,066).
Included are complex salts and calcium salts of low-, medium-, and high-molecular-weight acids and nut oil acids, as well as soaps. Another group of thickeners includes substituted ureas, phthalocyanines, indanthress and pigments such as perylimide, pyromellitodiimide, and ammeline. Preferred thickeners used in grease compositions are lipophilic clays in nature. Such thickeners are initially hydrophilic in nature, but by introducing long-chain hydrocarbon groups onto the surface of the clay particles, i.e. organic cationic surfactants such as onium compounds can be added to the surface of the clay particles prior to use as a component of the grease composition. It can be made from clays that can be converted to a lipophilic state by initial treatment with agents. Representative onium compounds are tetraalkylammonium chlorides such as dimethyldioctadecylammonium chloride, dimethyldibenzylammonium chloride, and mixtures thereof. This conversion method is well known to those skilled in the art and does not require further discussion and does not form part of the present invention. More specifically, clays useful as starting materials in producing thickeners for use in grease compositions include naturally occurring, chemically unmodified clays. These clays are crystalline complex silicates and cannot be precisely described because they vary widely from one natural source to another. These clays are described as inorganic complex silicates such as aluminum silicates, magnesium silicates, barium silicates, etc. containing varying amounts of cation converting groups such as sodium outside the silicate lattice. Hydrophilic clays that are particularly useful for conversion to the desired thickening agents include montmorillonite clays such as bentonite, attapulgite, hectorite, illite, saponite, sepiolite, biotite, vermiculite, zeolite clays, and the like. . This thickener is the main component of the entire grease composition.
It is used in amounts of 0.5 to 30% by weight, preferably 3 to 15% by weight. Liquid fuels used include fuel oil, diesel oil, gasoline and alcoholic fuels such as methanol, ethanol, or mixtures thereof. Solvents are suitable for all the above reactions. Solvents that can be used include hydrocarbon solvents such as toluene, benzene, xylene, etc., alcoholic solvents such as propanol, butanol, pentanol, etc., and mixtures of hydrocarbon or alcoholic solvents and mixtures of hydrocarbon and alcoholic solvents. Example 1 1,2-Hexadecanediol Borate 86 g of 1,2-hexadecanediol and 200 g of toluene solvent were placed in one reactor equipped with a stirrer, heater, and Dean-stark tube with condenser. I entered. The contents were heated to 80-90°C to dissolve the diol and about 11 g of boric acid was added. Leave the mixture for about 4 hours or more until water stops forming.
Heat to 155℃. Approximately 9 ml of water was removed by azeotropic distillation. The solvent was removed by vacuum distillation and the product was filtered through diatomaceous earth at 100°C. The product appeared waxy after cooling. The borate product is believed to have the following structure.

[expression] and

[Formula] (wherein R=C ₁₄ H ₂₉ ) Example 2 1,2-dodecanediol borate (high boron content) Approximately 151 g of 1,2-dodecanediol and toluene
1 equipped with a stirrer, a heater, a Jean-Starck tube with a condenser, and equipment for nitrogen gas exchange.
was charged into a reactor. The contents were heated to 75°C and 45g of boric acid was added. The mixture was heated to 155° C. for over 5 hours until water evolution ceased. The solvent was removed by vacuum distillation and the product was hot filtered through diatomaceous earth. The product was a viscous, clear yellow liquid. Example 3 1,2-Dodecanediol Borate Approximately 303 g of 1,2-dodecanediol and 250 g of toluene were charged to one reactor equipped as described in Example 2. The contents were heated to 70°C and 62g of boric acid was added. The mixture was heated to 160° C. for over 6 hours until water evolution ceased. The solvent was removed by vacuum distillation and the product was hot filtered through diatomaceous earth. Example 4 1,2-Mixed _C15 - _C18 Alkanediol Borate (High Boron Content) Approximately 155 g of 1,2-Mixed _C15 - _C18 Alkanediol
and 130 g of toluene were charged to one reactor equipped as described in Example 2. Contents at 65℃
34g of boric acid was added. The mixture was heated to 160° C. for over 4 1/2 hours until water evolution ceased. The solvent was removed by vacuum distillation and the product was filtered hot through diatomaceous earth to give a white waxy solid after cooling. Example 5 1,2-Mixed _C15 - _C18 Alkanediol Borate Approximately 265 g of 1,2-Mixed _C15 - _C18 Alkanediol
and 200 g of toluene were charged into one reactor equipped as described in Example 2. 70 contents
It was heated to 0.degree. C. and 42 g of boric acid was added. The mixture was heated to 155° C. for more than 5 hours until water evolution ceased.
The solvent was removed by vacuum distillation and the product was filtered through diatomaceous earth at 100°C. The products of the examples were mixed to form a fully formulated 5W containing additives such as detergents, dispersants, antioxidants, etc.
-20 synthetic automobile engine oil and evaluated by low velocity friction device (LVFA) testing. Product Evaluation The compounds were evaluated as friction modifiers by the following tests. Low Velocity Friction Apparatus Description The Low Velocity Friction Apparatus (LVFA) is used to measure the friction of a test lubricant under various loads, temperatures, and sliding rates. The LVFA is mounted on a vertical axis and rotates on a 51.6mm ² (0.08in ² area) fixed and raised narrow circular SAE1020 steel surface.
Equipped with SAE1020 flat steel surface (3.8cm diameter).
Both surfaces are submerged in the test lubricant. Friction between steel surfaces is measured as a function of the sliding velocity at a lubricant temperature of 121°C. Friction between rubbing surfaces is measured using a torque arm strain gauge system. The output of the strain gauge, calibrated to equal the coefficient of friction, is directed to the Y axis of the X-Y grapher. The speed signal from the tachometer generator is directed to the X-axis. The piston is supported by air bearings to minimize external friction. The normal force exerted on the rubbing surface is regulated by air pressure at the bottom of the piston. The drivetrain features an infinitely variable hydraulic transmission driven by a 373W (1/2 horsepower) electric motor. To change the sliding speed, the output speed of the transmission is adjusted by a lever-cam motor arrangement. Method: Place the rubbing surface and 12-13 ml of test lubricant on the LVFA. A load of 1756 kPa (240 psig) is applied and the sliding speed is maintained at 122 m/s (40 fpm) for several minutes at ambient temperature. Sliding speed, 1.5~12.2m/s (5~40fpm,
A plot of the friction coefficient is obtained in the range of 25195 rpm). A minimum of three measurement points is obtained for each tested lubricant. The test lubricant and specimen were then heated to 121°C and one more measurement set was obtained, bringing the system to 121°C.
°C, 240psi and sliding speed 12.2m/s (40fpm)
drive for 50 minutes. Then measure the speed vs. Uk
1756, 2170, 2859 and 3549kPa (240, 300, 400
and 500 psig). A freshly polished steel specimen is used for each run. Steel surface is 0.1~0.2μm
Grind parallel to (4-8 microinches). The data obtained are shown in Table 1. The data in Table 1 records the percentage reduction in the coefficient of friction at two speeds. The friction reducing ester additive was evaluated in a fully formulated 5W-20 synthetic lubricant consisting of a package of additives including antioxidants, detergents and dispersants. The oil had the following generality. Viscosity 100℃ 6.8cs 〃 40℃ 36.9cs Viscosity index 143

【table】

[Table] Ndiol
The results clearly show that hydrocarbyl borate vicinal diols are far superior friction reducers. For example, boric acid 1,2-mixture C ₁₅ of Example 5
-C ₁₈ alkanediol reduces the coefficient of friction by 40% to 28% even when used at only 1/2%. The products of this invention were tested in a catalytic oxidation test of lubricants using 200'' solvent paraffinic neutral mineral oil as the base oil.The test lubricant compositions were
Air flow was bubbled into the composition at a rate of 5 per hour. Present in the composition were metals commonly used as engine construction materials. That is, a 100.6 cm ² (15.6 sq.in) sandblasted iron wire, b 5.03 cm ² (0.78 sq.in) copper wire, c 561 cm ² (0.87 sq.in) aluminum wire, and d. Oil inhibitors ^are evaluated on the basis of prevention of acid formation caused by oxidation or oil degradation as measured by neutralization number (NN) and kinematic viscosity. Ru.

[Table] The results clearly show that borates are effective in controlling the increase in viscosity and the increase in neutralization number in moderately harsh conditions.

Claims (1)

Claims: 1. A liquid fuel or lubricant composition comprising: 1 a major amount of a fuel or lubricant; and a friction-reducing or oxidation-reducing amount of boric acid hydrocarbyl vicinal diol containing 10 to 30 carbon atoms; thing. 2. The composition according to claim 1, wherein the hydrocarbyl is decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl or eicosyl. 3 The agent used to treat the vicinal diol with borate has the formula: (RO) _x B(OH) _y where R is a C ₁ -C ₆ alkyl group, x is 0-3,
The composition according to claim 1 or 2, wherein y is 0-3, and the sum of x and y is 3. 4. The composition according to claim 3, wherein the drug contains boric acid. 5. Claim 1 in which the fuel is a hydrocarbon liquid fuel, an alcohol fuel, or a mixture thereof.
The composition according to any one of Items 1 to 5. 6. The composition of claim 5, wherein the hydrocarbon liquid fuel comprises fuel oil, diesel oil, gasoline or a mixture thereof. 7. The composition of claim 5, wherein the alcohol fuel comprises methyl alcohol, ethyl alcohol or a mixture thereof. 8. The composition according to claim 1, wherein the lubricant comprises a mineral lubricating oil, a synthetic lubricating oil, a mixture thereof, or a grease thereof. 9. The composition according to any one of claims 1 to 8, wherein the diol is 1,2-hexanediol. 10. The composition according to any one of claims 1 to 9, wherein the diol is 1,2-dodecanediol. 11. A composition according to any one of claims 1 to 10, wherein the diol is a 1,2-mixed _C15 - _C18 -alkanediol.