CA1198726A - Borated hydroxyl-containing compositions and lubricants containing same - Google Patents

Abstract

BORATED HYDROXYL-CONTAINING COMPOSITIONS
AND LUBRICANTS CONTAINING SAME

ABSTRACT OF THE DISCLOSURE

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

BORATED HYDROXYL-CONTAINING COMPOSITIONS
AND LUBRICANTS CONTAINING SAME

The invention relates to lubricant and liqui~ fuel compositions. In particular, 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 comoustion engines.
It provides for a liquid fuel or lubricant composition comprising a major ~mount of fuel or lubricant and a ~riction-reducing or anti-oxidant amount of a borated hydlocarbyl vicinal diol containing from 10 to 30 carbon atoms.
Alcohols are well known fGr their lubricity properties when formulated into lubrioating 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 ~ound wi~ L~ad use a~ hri~;ty additives. U.S. Patent

2,788,326 ~ s~ some of the e~ters suitable ~or the presenb i~vention, e.g. glyoerol manooleabe, as ~unor ~I~V~ Ls of Jl~hr;~ting oil c ~ ~;tions. U.S. Patent 3,235,498 ~;~çln~, amon~ other~ the same es~er as just mentioned, as an additi~e to other oils. u.S.
Patent 2,443,578 teaches esters ~hexein ~he free l~y~xyl is found in the acld portion, as for ~x~mrl~ in ta ~ ic acid.
The above patents, as are numercus others, are directed to the use of such esters as additives. Other patents~ such as UOS.
patents 2,798,083; 2,820,014; 3,115,519; 3,282,971; and 3,309;318 as well as an article by R. R. Barne~ et al. entitled ~Synthetic Ester Lubricants" in Lubrication En~ineerinq, August, 1975, pp. 454-457, teach lubricants prepared from polyhydric alcohols and acid containing no hydroxyl other than those associated with the acid fL!nctioh.
So far as is known, no effort has been made to employ borated hydrocarbyl vicinal diols as a fuel or lubricant additive. It is known that borated hydrocarbyl and borated aliphatic diols are known 2~i j for other uses. For example, U.S. Patent 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-cor,taining compound.
It has now been found that boration of these long-chain alkyl terminal vicinal diols significantly improves frictio~ reducing properties and imparts an anti-oxidant component to these novel c- r-~;tions. In addition to the friction-reducing properties described, the 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. Furthermore, the compositions also have significantly greater friction-redu~ing ~Lu~tLLies~ higher viscosity indices and good low temperature characteristics and solubility characteristics when used in low additive concentrations than do other known additives.
The hyd¢ocarbyl vicinal diols contemplated for use in this invention are hydrocarbyl diols having vicinal hydroxyls. They have the formula:
R~-OH)2 wherein 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 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 ~. Am. Chem. Soc., 689 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. Pa~nts 2,411,762, 2,457,329 and 2,455,892.

The diols can also be prepared via catalytic epoxidatiorl of an appropriate olefin followed by hydrolysis to form the appropriate vicinal diol.
~ he preferred borated vicinal diols contain 12 to 20 carbon atoms. Below a carbon number of 12~ friction-reducing properties are significantly reduced. Above a carbon number of 20, solllhillty constraints become significant. Preferred are the C14-C17 hydrocarbyl groups in which solubility, frictional characteristics and other properties are maximized.
Among the 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-miYed C15-C18-alkarediols 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 fTom 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 o~ten preferred to the single diol.
Reaction with the boron compound of the ~ormula (RO)xB(OH)y where R is a Cl to C6 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 temperaturcs of 90C to 263C or more can be used, but 110 to 200C is preferred.
Reaction times can be 1 to 24 hours and more. Up to a stoichiometric amount o~ boric acid can be used, or an excess thereof can be used to produce a derivative containing from about û.1% to about 10% of boron. At least 5 to lû% o~ the available hydroxyl groups o~ 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 ~ydroxyl groups) can also be charged to the reaction medium resulting in a 1~..~.

7~i product containing the stated amount of boron. The boronated diols can also be borated with a trialkyl borate such as tributyl borate9 often in the presence of boric acid. Preferred reaction temperatures for boration with the borate will range from 180C to 280C. Times can be from 2 to 12 hours, or more.
As disclosed hereinabove, the borated esters are used with lubricating oils to the extent of from 0.1% to 10~ by weight of the total composition. Furthermore, 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 wi~h the esters herein ~;srlosed 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 hy~LocaIbyl carboxylate ester fluids. The other synthetic oils, which can be used alone with the borate~ compounds of this invention, or which can be mixed with a mineral or synthetic hydrocarbon oil, include (1) fully esterified ester oils, with no ~ree hydroxyls, sucn as pentaerythritol esters of ,oca~boxylic acids having 2 to 20 carbon atoms, trimethylolpropane esters of monoca~oxylic acids having 2 to 20 carbon atoms~ (2) polyacetals and

(3) siloxane fluids. Fspeci~lly useful among the synthetic esters are those made from polyc2rboxylic acids and monohydric alcohols. More preferred are the ester ~luids made by fully esterifying pentaerythritol1 or mixtures thereof with di- and tripentaerythritol, with an aliphatic monocarboxyl~c acid containing ~rom 1 to 20 carbon atoms, or mixtures of such acids.
A wide variety of thickening agents can be use~d in the greases of this invention. Included among the thickening agents are alkali and alkaline earth metal soaps of fatty acids and fatty F-1~63 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, steaxin, cottonseed oil acids, oleic acid, palmitic acid, myristic acid and hydrogenated fish oils.
Other 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.
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 chlorlde, dimethyl dibenzyl ammonium chloride and mixtures thereof.
This method of conversion, being well known to those skilled in the art, is believed to require no further ~;scussion, and does not form a part of the present invention. More specifically, 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 rlot subject to precise description, since they vary widely from one natural source to another. ThesP clays can be described as complex inorganic silicates ~87~6 such as aluminum silica-tes, magnesiurn silicates, barium silicates, and the like, containing, in addition to the silicate latticel 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.
l~ The 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.
In all reactions described hereinabove, a solvent is preferred. 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.

1,2-Hexadecanediol Borate 869 of 1,2-hexadecanedi~l and 2ûûg toluene sclvent was charged to a 1 liter reactor equipped with agitator, heater and Dean-Stark tube with condenser. The contents were heated up to 80-90C to dissolve the diol and approximately 119 boric acid was added. The mixture was heated up to 155C until water evolution stopped over a period of about 4 hours. Approximately 9 ml water was removed by azeotropic distillation. The solvent was removed by vacuum distillation and the product was filtered at 100C through diatomaceous earth. The product became waxy after cooling.
It is believed that the borated product included the following structures:

7~
F - l~ 63 H H
R - C lH2 R - C lH2 B/ and \ B

0/ \0 where R = C14H29 1,2-Oodecanediol Borate (High Boron Content) Approximately 151g o~ 1,2-dodecanediol and 1509 cf toluene were charged to a 1 liter reactnr eqll;pped with agitator, heater and 3ean~Stark tube with condenser and provision for using a nitrogen vapor space blanket. The contents were heated up to 75C, and 45g of boric acid was added. The mixture was heat~d up to 1s5oc over a period of 5 hou~s until water evolution stopped. The solvent was removed by vacuum distillation and the product was fi:l.tered hot through diatomaceous earth. The product was a viscous, clear yellow fluid.

1,2 Dodecandiol Approximately 303g of 1,2-dodecanediol and 2509 of toluene were charged to a 1 liter reactor equipped as described in Example 2.
The contents were heated up to 70C and 62g of boric aoid was added.
The mixture was heated up to 160C over a period of 6 hours until water evolution stopped. The solvent was removed by ~acuum distillation and the product was filtered hot through diatomaceous earth.

a~
.,~7~

1,2-Mixed C15~_18 Alkanediol Borate (High Boron Content) Approximately 1559 of 1,2-mixed C15-C18 alkanediols and 130g of toluene were charged to a 1 liter reactor equipped as described in Example 2. The contents were heated up to 65C and 349 of boric acid was added. The mixture was heated up to 160C over a period of ~ 1/2 hours until water evolution stopped The solvent was removed by vacuum distillation and the product was filter~d hot through diatomaceous earth, yielding a white waxy solid after cooling.

1,2-Mixed Cl ~ 18 Alkanediol Borate Approximately 2659 of 1,2-mixed C15~C18 alkanediols and 2009 of toluene were cnarged to a 1 liter reactor equipped as described in Example 2. The contents were heated to 70~C and 42g of boric acid was added. The mixture was heated up to 155C over a period of 5 hours until water evolution stopped. The solvent was removed by vacuum distillation and the product was filtered at 100C
through diatomaceous earth.
The product of the Examples were blended into a fully formulated 5W-~O synthetic automotive engine oil containing other additives, such as detergent, clispersant, anti-oxidant and the like additives and evaluated using the Low Velocity Friction ~pparatus (LVFA) test.
EVALUATION OF PRO~UCTS
The compounds were evaluated as friction modifiers in accordance with the following test.
LOW VELOCITY FRICTION APPARATUS
Description ~ he Low Velocity Friction Apparatus (LVFA) 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 mm2 (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 121C.
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 t~le Y axis of an X-Y plotter. The speed signal from the tachometer-generator is ~ed to the X-axis. To minimize external friction, the piston is supported by an air bearing. The normal force loa~ing the rubbing surfaces is regulated by air pressure on the bottom of the piston. The drive system consists o~ 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.
Procedure The rubbing surfaces and 12-I3 ml of test lubricant are placed on the LVFAo 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 (Uk) over the range of sliding speeds, 1.5 to l~2 m/s (5 to 40 fpm, 25-195 rpm), is obtained. A minimum o~ three measurements is obtained for each test lubricant. Then, the test lubricant and specimens are heated to 121C~ another set of measursments is obtained, and the system is run for 50 minutes at 121C, 240 psi and 12.2 m/s (40 fpm) sliding speed. Afterward, measurements of Uk vs. speed are taken at 1756, 2170, 2859 and 3549 kPa (240, }00, 400, and 500 psig). Freshly polished steel specimens are used for each run. The surface of the steel is parallel ground to ol to .2 ~m (4-8 mic~oinches).
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 ~riction-re~ ;n~ es~er additi~es ware evalua~ed in a fully formulated 5W-20 synthetic lubricating oil comprising an additive package including anti-oxidant, detergent and dis~eIsant.
The oil had the following general characteristics:
Viscosity lOO~C - 6.8cs Vi~cosity 40C - 36.9 cs Viscosity Index - 14~

F 1263 -1 n-TABLE l Friction Test Results Using Low Velocity Friction Apparatus Additive% Reduction in Coefficient Conc. inof Friction in LVFA at Example Additive Base Blend0.025 m/s0.152 m~s Base Blend Fully formulated engine oil --l Borated 1,2- l 45 30 hexadecanediol 0.5 41 32 0.~5 28 2 Borated 1,2- 2 33 22 dodecanediol l 45 35 ~high boron content) 0.5 34 27 eorated 1,2- l 37 27 dodecanediol O.S 37 31 Borated 1~2-mixed C,~_C1Q alkanediols 2 42 35 (~lgh ~oron content~ 0.5 33 27 Borated 1,2-mixed l 4~ 31 Cl5-Cl8 alkanediols 0.5 40 28 F-1?63 The results clearly show the borated hydrocarbyl vicinal diol to be a far superior friction reducerO For example, the use of only 1/2% of Example 5, borated 1,2-mixed C15 C18 alkanediols reduces the coefficient of friction by 40%/28%.
The products of this invention were tested in a catalytic oxidation test for lubr'cants, 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 163C for 40 hours. Present in the composition are metals commonly used as materials of engine construction, namely:
a. 100~6 cm2 (15.6 sq. in.) of sand-blasted iron wire, b. 5.03 cm (0.78 sq~ in.) of polished copper wire7 c. 5.61 cm2 (0.87 sq. in.) of polished aluminum wire, and d. 1.08 cm (0.167 sq. in.) of pûlished lead surface.
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.

Catalytic Oxidation Test 40 Hours ~ 163C

Additive % Increase Conc. in Viscosity, ~eutralization Additive Wt. % KV at 100C Number ~ase Oil Only -- 67 3.62 Example 1 1 22 1.96 3 38 1.60 Example 2 0.25 18 1.95 0.5 19 1.71 1 15 1.32 3 4 0.55 Example 3 Example 4 1 11 2.10 3 15 1.89 Example 5 1 13 2.43 3 17 2.~4 The results clearly show the effectiveness of the borates at controlling viscosity increase and neutralization nu~ber increase under somewhat severe oxidation conditions.

Claims (7)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A liquid fuel or lubricant composition comprising a major amount of a fuel or lubricant and a friction-reducing or antioxidant amount of a borated hydrocarbyl vicinal diol comprising 1,2-mixed C15-C18 alkanediols.

2. The composition of claim 1 wherein the agent used to borate the vicinal diol has the formula (RO)xB(OH)y wherein R is a C1-C6 alkyl group, x is 0 to 3 and y is 0 to 3, the sum of x and y being 3.

3. The composition of claim 2 wherein the agent comprises boric acid.

4. The composition of claim 1 wherein the fuel comprises a liquid hydrocarbon fuel, an alcohol fuel or mixtures thereof.

5. The composition of claim 4 wherein the liquid hydrocarbon fuel comprises a fuel oil, diesel oil, gasoline or mixtures thereof.

6. The composition of claim 4 wherein the alcohol fuel comprises methyl alcohol, ethyl alcohol or mixtures thereof.

7. The composition of claim 1 wherein the lubricant comprises a mineral lubricating oil, a synthetic lubri-cating oil, mixtures thereof, or greases therefrom.