JPS59190996A - Boronated epoxides, lubricating agent and fuel containing same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a class of novel compounds and their use in lubricants or liquid fuels as anti-friction agents, antioxidants or anti-wear corrosion inhibitors (e.g. rust inhibitors for copper). be.

It is known that sliding or friction metal or other solid surfaces are susceptible to corrosion under extremely high pressure conditions. Corrosion is particularly severe in modern engines where high temperatures and high contact pressures are common. Under these conditions, even with current generation lubricants, severe metal surface erosion occurs unless durability or anti-corrosion additives are present.

Friction is also a problem whenever two surfaces are in sliding or frictional contact. Friction is significant because in internal combustion engines and related power train configurations, a significant amount of the loss of theoretical mileage that could be gained from a gallon of fuel is directly attributable to friction.

Certain epoxides have been used in lubricants.

For example, US Pat. No. 4,244,829 describes the use of epoxidized fatty acid esters as lubricating substances in lubricating oils.

The present invention is based on the general formula: % formula % (wherein R, R', R2 and R3 are hydrogen or C8
-C3o hydrocarbyl group, at least one of which is a hydride 80 carbyl group), is combined with boric acid, boron oxide, or an alkyl borate (in the formula , X is 1 to 6, y is O to 2, the sum of X and y is 3, and R is an alkyl group consisting of 1 to 6 carbon atoms). The present invention provides a compound that

The present invention also provides a lubricant or liquid hydrocarbon fuel composition comprising a lubricant or fuel and a suitable amount of the product as a lubricant or antifriction agent.

As mentioned above, the compounds of the present invention are made by reacting epoxides with boric acid or alkyl borates. These products are primarily borate esters,
Products that may also be included are epoxide dodecane or the corresponding borate ester resulting from the reaction of a low polymer with a boron compound. The range of epoxides mentioned above includes 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxytantadecane, 1,2-epoxyhexadecane,
Includes 1.2-epoxyheptadecane, 1.2-epoxyoctadecane, 1.2-epoxyeicosane, and mixtures thereof. Hydrocarbyl means an alkyl, aryl, cycloalkyl or cycloalkenyl group of 8 to 30, preferably 10 to 22 carbon atoms. Preferably, the Hyde 80 carbyl group is an alkyl group.

As mentioned above, the boron compound used is boric acid, boron oxide or an alkyl borate, of which boric acid is preferred. Alkylborates include mono-, di- and trialkylborates such as mono-, di- and triethylborate.

The reaction is about 80tZ' to about 260C1, preferably about 1
It is carried out at 1 DC to about 18 On. The choice of reaction temperature is determined in most cases by the side reactants and whether or not a solvent is used. In carrying out this reaction,
Is the amount of reaction raw material epoxide? The molar ratio of the diboron compound is from 02:1 to 4:1, preferably from 05:1 to 2:
It is preferable to select 1. For example, in the reaction illustrated in Example 1, the molar ratio is about 6:2.

The epoxide may be partially borated or reacted with excess boronating agent to form a composition containing from 0.1% to 10% by weight or more of boron.

Although atmospheric pressure is generally preferred, it is advantageous to conduct the reaction at 101 to 506 kPa. Additionally, solvents may be used if conditions permit. Generally, relatively non-polar, non-reactive solvents can be used, including benzene, toluene, xylene and 1,4-dioxane. Other hydrocarbon and alcoholic solvents (propa/-/l/.

(including zutanol, etc.) can also be used.

Mixtures of alcoholic and hydrocarbon solvents can also be used.

Reaction time is not critical. Therefore, the main step of any system can be carried out for 1 to 20 hours.

Of particular importance, according to the invention, an oily lubricating medium consisting of liquid oil in the form of mineral oil, synthetic oil or a mixture thereof or in the form of a grease (the oils mentioned above are used as carriers) is of particular importance. It is possible to improve the anti-oxidation and corrosion and high temperature resistance properties of substances. Mineral oils (including paraffinic petroleum and naphthenic petroleum, as well as mixtures thereof) commonly used as lubricants or grease carriers may be used, for example, at 38 tr in 5.
8 cs (45 SSU) to 1300 cs (600
0SSU), preferably Z6 to 54 at 99tT
cs (50 to 2505 SU), with a suitable lubricating viscosity range. These oils have a viscosity index of about 100 or greater. A viscosity index of about 70 to about 95 is desirable. These oils have an average molecular weight of about 250 to about 800. When a lubricant is used in the form of a grease, the lubricant is generally added in proportion to the overall grease composition, after determining the required amounts of thickeners and other additive ingredients to be included in the grease formulation. Use enough.

Various thickeners can be used in the grease of the present invention. These thickeners include alkali and alkaline earth metal soaps of fatty acids and lipids having from 12 to about 60 carbon atoms per molecule. Typical metals are sodium, lithium, calcium and barium. Examples of lipids are stearic acid, hydroxystearic acid, stearin, cottonseed oil acid, oleic acid, palmitic acid, myristic acid and hydrogenated fish oil.

Other thickeners include calcium stearate-calcium acetate (U.S. Pat. No. 2,197,263), barium stearate-barium acetate (U.S. Pat. No. 2,564,
No. 561), calcium stearate-calcium caprylate-calcium acetate complex (U.S. Pat. No. 2.999)
, 065), calcium caprylate-calcium acetate (U.S. Pat. No. 2,999,066) and low-1 medium-
1, including calcium and soapy salts and salt-soap complexes of high molecular weight acids and solid acids.

Other groups of thickeners consist of substituted ureas, phthalocyamines, indanthrenes, dyes (such as Ryllimitimide, pyromellidiimide and amylin).

Preferred thickening gelling agents used in grease compositions are essentially hydrophobic clays. Such thickeners can be produced from a viscosity that is initially hydrophilic in nature by converting it into a hydrophobic state. That is, long-chain hydrocarbon groups are added to the surface of the clay particles prior to use as a component of a grease composition, such as by pretreatment with an organic cationic surfactant such as an onium compound. It can be manufactured by introducing Typical onium compounds include quaternary alkylammonium fluorites such as dimethyldioctadecylammonium chlorite, dimethyldibenzylammonium chlorite, and mixtures thereof. The means for this conversion are well known to those skilled in the art.

Synthetic oils also work well. Typical synthetic oil vehicles are polyisobutylene, polybutene, hydrogenated polydecene, polypropylene glycol, yy+) ethylene glycol, trimethylolpropane ester, neoantyl and trimethyl esters,
ethylhexyl) sebacate, di(2-ethylhexyl)azimate, dibutyl phthalate, fluorocarbons, silicate esters, silanes, esters of phosphorus-containing acids, liquid urea, ferroracene derivatives, hydrogenated synthetic oils, linear polyphenyls, siloxanes and silicones ( polysiloxane), alkyl-substituted diphenyl ethers represented by butyl-substituted bis(p-phenoxyphenyl) ether, and phenoxyphenyl ethers.

However, it should be understood that the lubricant compositions contemplated in this invention may also include other materials. For example, corrosion inhibitors, extreme pressure additives, viscosity index improvers, antioxidant aids, friction reducers, etc. can be used. Also, ferulates, sulfonates, succinimides 8, zinc dialkyldithiophosphates, vulcanized olefins, chlorinated hydrocarbons, over-based calcium and/or magnesium compositions, hindered phenols, amine antioxidants. etc. can also be used, but the invention is not limited to these. These materials do not diminish the value of the compositions of the invention. Rather, their addition serves to impart customized properties to the composition.

Mineral oil heat exchange fluids specifically contemplated according to the present invention are
Fine: has high thermal stability, high initial boiling point, low viscosity, high heat resistance and low corrosion tendency.

Additionally, the transmission fluid of the present invention is a highly refined petroleum base blended with V1 improvers, detergents, defoamers, and special additives to have controlled frictional or lubricity properties.

Various transmission design concepts require fluids with significantly different frictional properties, making it impossible for a single fluid to meet all demands. Fluids used in automatic transmissions for passenger cars and light trucks are defined in ASTM Research Report D-2: RR1005 for "Automatic Transmission Fluids/Dynamic Transmission Fluid Characteristics and Performance Specifications." The standard for low temperature and aircraft fluids is the US government standard M Engineering L-H'-5.
606A.

In addition, the oxidation and corrosion resistance of functional fluids such as hydraulic fluids, especially at high temperatures, is improved by the adducts of the present invention.

The fuel used for the purpose of the present invention is (1) diesel oil,
Liquid hydrocarbon oils, such as fuel oil and gasoline, (2)
Includes alcohol-based fuels such as methanol and ethanol, and (3) mixtures thereof.

Generally, the reaction products of the present invention have a desired degree of antifriction activity,
An amount effective to impart corrosion inhibitory activity, antioxidant activity, high temperature stability, or rust inhibiting activity is used. however,
In many applications, the compound will be about 0.0% of the total weight of the composition.
It is useful to use amounts of from 0.1% to about 10% (by weight), preferably from about 1% to about 5%.

Example 1 Mixture) Approximately 244 g of 1,2-epoxy-alkane (C15-C
18 mixture) (from Viking Chemical Company Vj
, kol, ○x15-18 and contains the following t1.2-epoxyalkane: 1.2
-Kodanzoxy CI5 alkane (28%), 1,2-epoxy C16 alkane (28%), 1,2-epoxy C1
6 alkane (28%), 1,2-epoxy C16 alkane (16%)), 100 g toluene and 42 g boric acid were placed in a 11 reaction vessel equipped with a stirrer, heater and Dean-Stark tube (with cooling tube). added. The contents were heated with stirring and bubbling N2 for about 5 hours until water production ceased. The solvent was removed by distillation in vacuo at 155C and the product was passed through diatomaceous earth at 1201:. Upon cooling, the product became a clear amber gel-like waxy solid.

Example 2 Approximately 212 g of 1,2-epoxytetradecane (commercially available as Vj, kol-ox 14 from Viking Chemical Company), 100!9 of toluene solvent and 42.9 of boric acid as described in Example 1 It was added to 11 reaction vessels equipped with similar equipment. The contents were mixed with N2 under stirring.
The mixture was heated for about 6 hours until water production ceased.

The solvent was removed by vacuum distillation at 160C and the product was
Passed through diatomaceous earth at 6DC. Upon cooling, the product was a clear viscous liquid that became a waxy solid upon cooling.

Example 3 Borated 1,2-deoxyhexadecane about 1
440.9 g of 1,2-epoxyhexadecane (commercially available from Kuhnion Carbide), 400 g of toluene, and 248 g of boric acid were added to a 11 reaction vessel equipped as described in Example 1. The contents were stirred and bubbled with N2 for 5 hours until water formation ceased.
Heated at 0C. The solvent was removed by vacuum distillation at 1 soc and the product was passed through a diatomaceous filter at 120C. Upon cooling, the product became an amber waxy solid.

Example 4 Borated 1,2-epoxyhexadecane 1.2
- Epoxyhexadecane was borated using the general method described in Example B. However, the ratio of the reaction materials is as follows: 1440.9 of 1,2-epoxyhexadecane, 500 I of toluene and 375 g of boric acid. The product became an amber waxy solid upon cooling.

Example 5 -C18 mixture) Approximately 666 g of 1,2-epoxy-alkane (C1°-C
18 mixture) (as shown in Example 1), 250 g toluene, 680 g diluent process oil and 188 g boric acid were added to a reaction vessel equipped as described in Example 1. The contents were heated to 170 t:: under stirring and bubbling with N2 for 5 hours until water formation ceased. The solvent was removed by vacuum distillation and the product was passed through a diatomaceous filter. The product became waxy upon cooling.

Example 6 (C18 Mixture) 1.2-Epoxyalkane (C]5'+8 Mixture) was borated as generally described in Example 5. However, the following reaction materials are used: 366 g of 1,2-epoxy-alkane (C1, -C18 mixture), 400 g
Toluene, 4 and 5! j diluent process oil, 255g
of boric acid and 10 ml of tutanol. The product became somewhat cloudy upon cooling.

Evaluation of Compounds of the Invention The compounds were evaluated using a low velocity friction apparatus (LVFA) in a prepared 5L-20 synthetic automotive engine oil containing additives consisting of antioxidants, dispersants, and detergents. The test compounds were used at 1%, 2% and 4% by weight of the total oil weight.

Description A Low Velocity Friction Apparatus (LVFA) is used to measure the coefficient of friction of a test lubricant under various loads, temperatures, and sliding speeds. LVFA is flat SAE 1020
It consists of a steel surface (diameter 3.8 crrt), which is connected to the drive shaft and rotates on a stationary raised-bottom narrow ring-shaped SAE 1020 steel surface (52.4 mm2). Both surfaces are submerged in the lubricant being tested. Friction between steel surfaces is measured as a function of sliding speed at a lubricant temperature of 121C. The friction of the rubbing surfaces is measured using a torque arm strain gauge system. The output of the strain gauge is calibrated to be equal to the friction; the number of threads, and is the Y axis of the XY block. The speed signal from the tachometer generator is along the X-axis. The piston is supported by air bearings to minimize external friction.

The normal force loading on the grinding surfaces is regulated by air pressure at the bottom of the piston. Drive system 373W
('/2 HP) Consists of an infinitely variable speed hydraulic transmission powered by an electric motor. To vary the slip speed, the transmission output torque is adjusted by a lever-cam motor arrangement.

Method: Rub the surface and 12 to 13 ml of the test lubricant
Place it on VFA. 1656 kPa (240psi)
Increase the load and reduce the sliding speed to 0 for 2 to 6 minutes at an appropriate temperature.
．． 2 m/s (40 vpm). The plot of friction coefficient against speed is 1656, 2070.2760 and 3450kPa (240, Do, 400 and 5
0 D psi). Freshly polished steel samples were used for each test. The results in Table 1 report the % reduction in friction compared to untreated oil.

In other words, the above formulation was tested without the addition of the compound of the invention, and this served as the basis for comparison. The result is 121C1
Obtained at 3450 kPa (500 psi).

Table 1 Example 1 2 19 11 Example 22'15 9 Example 3 2 13 7 Example 5 4 30 22 Copper strip corrosion testing was also conducted according to ASTM D130-80. The results are shown in Table 2.

An anti-corrosion effect was observed in the 200″-ξ rough-in neutral mineral oil solvent.

Table 2 This product was further evaluated for oxidative stability. In many cases, improved oxidative stability was observed over the base oil. Basically, the test lubricant was blown with air flow at a rate of 51 per hour for 24 hours at 219C. Present in the composition are samples of metals commonly used in engine manufacturing, namely iron, copper, aluminum and lead.

This test method is disclosed in detail in US Pat. No. 6,682,980. This is shown to be more effective for control than improving the viscosity index or neutralization value (or both). Table 6 shows the results.

Table 6 Percentage applicants Mobil Oil Corporation (4 others)

Claims (9)

[Claims] (1) General formula: (wherein R2R1, R2 and R3 are hydrogen or a hydrocarbyl group having 8 to 30 carbon atoms, at least one of which is a hydrocarbyl group) and , boric acid, boron oxide and general formula: % formula % () (wherein, X is 1 to 1, y is O to 2, the sum of X and y is 6, and R is 1 to 6 A reaction product obtained by reacting a boron compound selected from the alkyl borates of the alkyl radicals having 5 carbon atoms. (2) The product according to claim (1), wherein the hydrocarbyl group is an alkyl, aryl, cycloalkyl or cycloalkenyl group. (3) Epoxide 9 is 1,2-epoxydecane, 1
,2-Ection+('Xydodecane, 1,2-epoxytetradecane, 1,2-EpoxyR-ntadecane, 1,2-Epoxyhexadecane, 1,2-Ectiond-oxyheptadecane, 1.2-Epoxyoctadecane, 1 , 2-epoxyeicosane or a mixture thereof. (4) A product according to claim (1) in which an epoxide is reacted with boric acid. (5) A lubricant or liquid fuel composition comprising a lubricant or fuel and an anti-friction additive according to any one of the above claims. (6) The composition according to claim (5), wherein the lubricant is mineral oil, synthetic oil, grease, or a mixture thereof. (7) The composition according to claim (5), wherein the liquid fuel is a liquid hydrocarbon fuel. (8) The composition according to claim (7), wherein the liquid hydrocarbon fuel is diesel oil, fuel oil, or gasoline. (9) The composition according to claim (5), wherein the liquid fuel is an alcohol fuel. 00) The composition according to claim (9), wherein the alcohol fuel is methanol or ethanol.