|1.||A reaction product suitable for use as __ι_lti_^χ£ional aπtioxidant/ant_Lrust/aπtiwear lubricant additives prepared by reacting (1) a hydrocarbyl substituted hydroquinone or resorcinol with (2) an alkoxylated alcohol or mixture of alkoxylated alcohols and (3) a boronating agent as described below: Mixed Borates where R is ^ to C3Q hydrocarbyl, R~ is C_ to C0 hydrocarbyl and optionally containing sulfur, nitrogen, phosphorus and or oxygen, R is C. to C3Q hydrocarbyl, and optionally σcntaining sulfur, nitrogen, phosphorus and or oxygen, x is an integer varying from 1 to 20, and y is an integer varying from 0 to 3.|
|2.||The product of claim 1 where the boronating agent is selected boric acid, metaborates, and trialkyl borates.|
|3.||The product of claim 2 where the boronating agent is boric acid.|
|4.||The product of claim 1 where reactaπt (1) is resorcinol or hydrocarbyl substituted resorcinol.|
|5.||The product of claim 1 where reaσtant (1) is hydroquinone or hydrocarbyl substituted hydroquincne.|
|6.||The product of claim 1 where the alkoxylated alcohol is mixed triethoxylated dα_teca~olpentadecanol.|
|7.||The product of claim 1 where the reactaπts are hydroquinone, triethoxylated mixed dodecarolpeπtadecanol, and boric acid.|
|8.||The product of claim 1 where the reactaπts are resorcinol, triethyαxylated mixed c x__canolpeπtacecanol and boric acid.|
|9.||A process for preparing mixed alkoxylated alccholhydroq inαne/__esorcinol borates suitable for use as ιrι_dti_unσtional aπtiαxidarrt/aπtirust/antiwear lubricant additives coπprising reacting (1) a C . hydrocarbyl hydroquinone or resorcinol (2) an alkoxylated alcohol having the structure R—(OR ) —QH where R is C. to C3Q hydrocarbyl, and R is C_ to C20 hydrocarbyl and cptionally containing sulfur, nitrogen, phosphorus and/car oxygen, and where x is an integer varying from 1 to 20 or mixture thereof and (3) a boronating agent, the reaction being carrried cut at taπperaturesof from 35* to 250*C at ambient or slightly higher pressure with molar quantities, less than molar quantities and more than molar quantities of the boronating agent.|
|10.||The process of claim 9 where the boronating agent is selected nun borix acid, metaborates and trialkyl borates.|
|11.||The process of claim 10 where the boronating agent is boric acid.|
|12.||The process of claim 9 where reactaπt (1) is resorcinol or hydrocarbyl substituted resorcinol.|
|13.||The process of claim 9 where reactaπt (1) is hydroquinone or hydrocarbyl substituted hydroquinone.|
|14.||The process fo claim 9 where the alkoxylated alcohol is mixed triethoxylated dodeca~olpeπtadec~_nol.|
|15.||The process of claim 9 where the reactaπts are hydroquinone, txiethαxylated mixed dodecanolpeπtadecanol, and boric acid.|
|16.||The process of claim 9 where the reactaπts are resorcinol, triethαxylated mixe cpcjecarolpeπtadecanol and boric acid.|
|17.||The process of claim 9 where said process is a one pot, onestep process.|
|18.||A c πposition coπprising a major amount of an oil of lubricating viscosity or grease or other solid lubricant prepared therefrom and a minor multifunctional aπticxidant/antlrust/aπtiwear amount of from 0.01 to 10 by weight of the total coposition of a mixed alkoxylated alccholhydroquinone or alkoxylated alcoholresorcinol borate prepared as described below: Mixed Borates where R is C. to C3Q hydrocarbyl, R1 is C2 to C2Q liydrocarbyl and optionally ∞πtaining sulfur, nitrogen, phosphorus anϊ/or oxygen, R is C. to C30 hydrocarbyl, and optionally containing sulfur, nitrogen, phosphorus and or cocygen, x is an integer of from 1 to 0 20, and y is an integer of frαn 0 to 3.|
|19.||The ccnpositicn of claim 18 whrein the boronating agent is selected from boric acid, metaborates, and trialkyl borates.|
|20.||the ccnpositicn of claim 18 wherein the boronating 5 agent is boric acid.|
|21.||The ccnposition of claim 19 where a boronating agent other than boric acied is used, the boronating agent being selected metaborates and trialkyl borates.|
|22.||The cαπposition of claim 18 where the alcohol is a mixed triethαxylated alcohol.|
|23.||The ccπpositiαn of claim 21 where the sai alochol is triethαxylated mixed dodecanolpeπtadecanol.|
|24.||The ccnpositicn of claim 18 where the reactaπts are resorcinol, triethαxylated mixed dodecanolpeπtadecanol and boric acid.|
|25.||The ccnpositicn of claim 18 where the reactaπts are hydroquinone, triethαxylated mixed dcctecanolpeπtadecanol and boric acid.|
|26.||The exposition of claim 18 where molar quantiti.es, less than molar quantities or more than molar quantities of boronating agent are used.|
|27.||The composition of claim 18 where oil of lubricating viscosity is selected frcm mineral oilts, synthetic oils and mixtures thereof.|
|28.||The ccnpositicn of claim 27 where the oil is a mineral oil.|
|29.||The ccnpositicn of claim 27 where the oil is a synthetic oil.|
|30.||The ccnpositicn of claim 27 where the oil is a mixture of synthetic and mineral oils.|
|31.||The ccnpositicn of claim 18 where the ccnpositicn is a grease ccnpositicn.|
|32.||The ccnpositicn of claim 18 where the oil of lubricating viscosity or grease contains frcm 0.01 to 10 wt % of additive oil.|
|33.||The ccnpositicn of claim 31 where the grease is synthetic and or mineral oil lithium ccπplex thickened grease.|
|34.||The composition of claim 18 containing as an additional additive ccπponeπt a phscphorυs .and/or sulfur containing product.|
|35.||The ccnpositicn of claim 34 where the additional •_a.pu._ent is a phosphorodithioate.|
|36.||The ccnpositicn of claim 33 where the phosphorodithioate is a xinc dihydrocarbyl phcephorodithioate or an ashless nonmetallic dihydrocarbyl pέ_csphorodithiαate.|
|37.||A process for improving the fuel exonαπy of an internal combustion engine, ocnprising contacting the moving parts of said engine witha ccnpositicn as described in claim 18.|
|38.||A process for improving the dropping point, and or oxidative stability of a metal or nonmetal hydroxyl containing soap thickened grease by blending therein a minor amount of an additive product as described in Claim 18.|
|39.||Use of frcm 0.01 to 10% by weight of the total composition of a reaction product as defined in claim 1 as an aιτticxtddnt/a~ιtir_^aπtiwear additive in a exposition apprising a major amount of an oil of lubricating viscosity or grease or other solid lubricant prepared therefrom.|
This application is directed to nov»sl ackϋtive products cxjirprising mixed alkoxylated alcxtol-hydrojainone or resorcinol borates, a process of preparing such products, ccn_positicns ∞rrtaining such products .and methods of using such products. These products, when incorporated into oils of lubricating viscosity or greases thereof provide superior lubricant compositions having excellent antiαxidant activity and antiwear performance.
Lubricants such as lubricating oils and greases are subject to oxidative deterioration at elevated teπperatures or upon prolonged exposure to the elements. Such deterioration is evidenced, in many instances, by an increase in acidity and in viscosity and, when the deterioration is severe enough, it can cause metal parts to corrode. Antioxidants or oxidation inhibitors are used to minimize the effects of oil deterioration that occur. The degree and rate of oxidation will depend on temperature, air and oil flow rates and, of particulεtr iπportanoe, on the presence of metals that may catalytically pr nσte oxidation. Antioxidants generally function by prevention of chain peroxide reaction and or metal catalyst deactivation.
Water (moisture) is another critical problem. In spite of even extraordinary precautionary efforts water is found as a film or in minute droplets in vessels cx__τtai_ning various hydrocarbon distillates. This brings about ideal cx_nditions for corrosion and damage of metal surfaces of the vessels .and the materials contained therein. Also in the lubrication of internal ccanbustion engines, for example, quantities of water are often present as a separate phase within the lubricating system. Another serious problem in respect to metallic surfaces in
contact with adjacent metallic surfaces is wear caused by the contact of such surfaces.
One material capable of sim.1f~τ_eσusly and effectively coping with these problems is highly desireous. It has now been found that the use of these novel mixe hydrocμinαne or resorc-_nol"-a_Lkoxylated alcohol borates provides exceptional antiαxidant, antiwear and corrosion inhibiting activity with potential antifatique, friction reducing, antirust and high teπperature stabilizing properties. The use of hydroquinones and resorcinols has been well kncwn because of their aπtiαxidaπt properties in a variety of petroleum and non-petroleum products.
The use of borates has found extensive application in such diverse areas as grease additives, brake and hydraulic fluids and fu-≥l and combustion additives.
The use of a___koxylated alcohols or alkoxylated phenols has been widely reported as having beneficial multifuncticnal characteristics in a variety of fuel and lubricant applications. The present invention provides a reaction product suitable for use as multifunctional aπtioxiά_ t/antirust/aπtiwear lubricant additives prepared by reacting (1) a hydrocarbyl substituted hydroquinone or resorcinol with (2) an alkoxylated alcohol or mixture of alkoxylated alcohols and (3) a boronating agent as described below:
where R is C. to C hydrcx_ari~yl, R is C, to C hydrocarbyl and optionally containing sulfur, nitrogen, phosphorus and/or oxygen,
2 . . .
R is c. to C-- hydrocarbyl, and optionally cx_ ~ ttain__ng sulfur, nitrogen, phosphorus ancJ or oxygen, x is an integer varying frcm
1 to 20, and y is an integer varying from 0 to 3.
The present invention further provides a process for preparing mixed alkoxylated alcohol-hydroquincr_e/__esorcinol borates suitable for use as multifuricticnal antioxidant/ant__rust/antiwear lubricant additives comprising reacting (1) a C.-C-. hydrocarbyl hydroquinone or resorcinol (2) an alkoxylated alcohol having the structure R—(O-R ) —OH where
1 . R is C χ to C 30 hydrocarbyl, and R is C 2 to C 2Q hydrocarbyl and optionally containing sulfur, nitrogen, phosphorus and/or oxygen, and where x is an integer varying from 1 to 20 or mixture thereof a d (3) a boronating agent, the reaction being carrried out at t-aiperatures of from 35° to 250°C at ambient or slightly higher pressure with molar quantities, less than molar quantities and more than molar quantities of the boronating agent.
The present invention also provides a cαπposition comprising a major amount of an oil of lι_foriσating viscosity or grease or other solid lubricant prepared therefrcπi and a minor multifunctional antiαxidaι_t/ax±___-ιst/aπtiwear amount of from 0.01 to lόjlby weight of the total cαrposition of a mixed alkoxylated alccihol-hyd__oquinone or alkoxylated alcohol-resorcinol borate prepared as described below:
+ R-~(CHR ) χ — OH + lyao.. " Mixed Borates
where R is C. to C 3Q hydrocarbyl, R is C_ to C_ 0 hyά_αxarbyl and optionally containing sulfur, nitrogen, phosphorus and/or oxygen, R is G. to C_ 0 hydrocarbyl, and cptiαirially containing sulfur, nitrogen, phosphorus an-_i/ or oxygen, x is an integer varying from 1 to 20, and y is an integer varying from 0 to 3.
This application is directed to lubricant products derived from mixed alkoj~lated alcohol hyd-_oqι__i_rκ-ne/__esorcinol borates and to lubricant compositions containing small additive cor__entrations of mixed alkoxylated alcohol-hydroquinone borates or mixed alkoxylated alcohol-resorcinol borates. These novel σcπpσunds possess excellent antioxidaπt activity and multir&αnctonal antiwear performance. Aixordingly, this application is directed to the above referred to novel additives and to novel lubricant ccπpositions cant_a_Lning same and to their use. The present invention is also directed to the use of such products as an antioxidant/aπtiru_=*/aπt_iwear additive in a ccnposition coπprising a major amount of an oil of lubricating viscosity or grease or other solid lubricant prepared therefruu.
A process by which the additive products in accordance with the invention may be prepared is outlined below.
where R is C. to C 3Q hydrocaarbyl, vdiich indirtes tut is not limited to aliphatic, cyclic and aromatic groups, and can optionally contain sulfur, nitrogen, piios ~ _horus and or oxygen, R is C_ to C - hydrocarbyl, preferably C -C- ftydroczirbyl, R is C. to C 3Q hydrocarbyl, and can optionally contain sulfur, nitrogen, pho__pi orus and or oxygen, x is an integer of from 1 to 20, and y is an integer of from 0 to 3, with 1-2 being preferred.
For example, triethσxylated mixed dodec_ar_ol-pentadecar_ol (coπmercially cfctained frαn Shell Qiemical Coπpaπy as Neodol 25-3 triethαxylated mixed C --C 15 alcohols) was co-borated with hydroquinone or resorcinol to form mixed borate esters. Both the hydrcx~uinone and/or resorcinol moiety and the borate ester are believed to provide the basis for synergistic antiαxidant activity. The alkoxylated alcohol and borate ester are also believed to contribute additional aπtirust, de ergency and or friction reducing properties to the additives. Mthαugh applicants do not wish to be held to a particular theory, these benefical properties are believed to be enhanced as a result of this novel .Internal synergism. This internal synergism σonσept is believed to be applicable to similar structures coπtaάjiing hydroquinone or resorcinol borate ester and alkoxylated alcohol or alkoxylated phenol moieties within the same molecule.
The alkoxylated alcohol usually contains at least six carbon atoms to sixty carbon atoms. Preferred are such alcohols as dodecanol, pentadecartol and mixtures thereof.
Boric acid can be used as a boronating agent or metaborates, triakyl borates or any other suitable boronating agent may be employed. Suitable metaborates include but are not limited to tri.~eth.yl metaborate (triirethoxy_x>roxine) , triethyl metaborate, tributyl metaborate. Suitable trialkyl borates include but are not limited to trittethyl borate, triehtylborate, triiscprcyl borate (triiscprcpocxyborane), tributyl borate(trilbutoxyborane and tri-tert-butyl borate.
The reaction conditions are not believed to be critical. Conditions therefore may vary widely, depending upon such as whether or not a solvent is used. Suitable solvents include hydrocarbon solvents such as toluene and the like. The pressure may generally be ambient or slightly higher, if desired. The teπperature may vary from ambient or to about 35 β C to about 250 Φ C or reflux. An excess of one reagent or another can be used. An
excess of one reagent or another can be used. Molar quantities, less than molar quantities, or more than molar quantities of boronating agent can be used. Up to a 500% molar excess of boronating agent can be used. The additives may be incorporated into any suitable lubricating media which comprises oils of lubricating viscosity, e.g., mineral or synthetic; or mixtures of mineral and synthetic, or greases in which the aforementicned oils are employed as a vehicle or into such functional fluids as hydraulic fluids, brake fluids and power transmission fluids. In general, mineral oils and or synthetic oils, employed as the lubricant oil, or grease vehicle may be of any suitable lubricating viscosity range, as for exanple, from 45 SSϋ at 37.8'C (100'F) to 6000 SSϋ at 37.8 β C (100'F), and, preferably, from 50 to 250 SSU at 98.9'C (210*F) . These oils may have viscosity indices from below zero to 100 or higher. Viscosity indices from 70 to 95 are preferred. The average molecular weight of these oils may range from 250 to 800.
Hi ____tances where synthetic oils are desired in preference to mineral oils as the vehicle for the grease, or in combination therewith, various cuipounds of this type may be successfully utilized. Typical synthetic vehicles include polyiscbutylene, polybutenes, hydrogenated polydecenes, polypropylene glycol, polyethylene glycol, trimethylolpropane esters, necpeπtyl and peπtaerythritol esters, di(2-«thylhexyl) sebacate, di(2-ethylhexyl) adipate, dibutyl phthalate, fluαrocarbcns, silicate esters, silanes, esters of phc~~_horous-conta____~ig acids, liquid ureas, ferrocene derivatives, hydrogenated mineral oils, chain-type polyphenyls, siloxanes and siliccnes (polysiloxanes) , a___kyl-substituted diphenyl ethers typified fcy a butyl-substituted bis (p-phenαxy pheπyl) ether and phenαxy phenylethers.
The products of this application also show good coπpatibility when used in the presence of other additives in the lubricant cα ~ positions. Therefore, fully formulated lubricating oils may include a variety of additives (for their known purpose) such as dispersants, detergents, inhibitors, antiwear agents, antioxidaπt, antifoam, pour depressant and other additives including phenates, sulfonates and phosphates such as zinc dithicphoεphates, zinc dihydrocsarbyl phosphorc thioates and ashless non-metallic dihydrocarbyl phosphorodithioates. Where the lubricant is to be enployed in the form of a grease, the lubricating oil is generally enployed in an amount sufficient to balance the total grease coπpositicxi, after acxounting for the desired quantity of the thickening agent and other additive components to be included in the grease formulation.
When high teπperature stability is not a requirement of the finished grease, mineral oils having a viscosity of at least 40 SSϋ at 65.6'C (150°F) , and particularly those falling within the range frαn 60 SSϋ to 6,000 SSϋ at 37.8'C (100'F) may be enployed. The lubricating vehicles of the iπprσved greases of the present invention, containing the above described additives, are ccnbined with a grease forming quantity of a thic_cening agent. For this purpose, a wide variety of material?- axe dispersed in the lubricating vehicle in grease-fo lng quantities in such degree as to impart to the resulting grease coπpositicn the desired consistency. Exeπplary of the thickening agents that may be employed in the grease formulation are non-soap thickeners such as surfacemodified clays and silicas, aryl ureas, calcium cαπplexes and similar materials. In general, grease thickeners may be enployed which do not melt and dissolve when used at the required teπperature within a particular eπvirxx-neπt. Soap thickeners such as metallic (lithium or calcium) soaps including hydro.-- stearate and/or stearate soaps can be used. However, in
all other respects, any material which is normally enployed for thickening or gelling hydrocarbon fluids or forming greases can be used in preparing the aforementioned iπprσved greases in accordance with the present invention. Included among the preferred thickening agents are those containing at least a portion of alkali metal, alkaline earth metal or amine soaps of hydroxyl-cαntaining fatty acids, fatty glycerides and fatty esters having from 12 to 30 carbon atcms per molecule. The metals are typified by sodium, lithium, calcium and barium. Preferred is lithium. Preferred meπbers
.among these acids and fatty materials are __2-hydroo-~3tearic acid and glycerides containing 12-hydrcκystearates, 14-hydrαxystearic acid, 16-hydrαxystearic acid and 6-hydrαxystearic acid.
Included among the other useful thickening agents are alkali and alkaline earth metal soaps of methyl-12-hydrOxystearate, diesters of a C. to C-. dicarbαxylic acid and tall oil fatty acids. Others alkali or alkaline earth metal fatty acids corrtaining from 12 to 30 carbon atcms and no free hydrαxyl may be used. These include soaps of stearic and oleic acids.
As has been diclosed hereinabσve, the reaction products are useful as multifunctional antiwear/ar icxόdar /aπtrirust agents. They are added to the lubricating medium in amounts sufficient to iπpart such properties to the lubricant. More particularly, such properties will be imparted to the lubricant by addition from 0.01% to 10% by weight, preferably from 0.05% to 3%, of the neat product.
The following example is exemplary and not intended as limitations.
Example 1 i^rαximately 55g hyάroguinone, 61.8g boric acid and 336g of triethαxylated mixed dodecanol-peπtadecanol (ooπmercially
obtained from Shell Chemical Cαπpaπy as Neodol 25-3) and 200 ml toluene were mixed in a reactor equipped with heater, stirrer and Dean-Stark trap. The reactants were heated at 125 * C over a period of six hours during which 41g water was azeσtrαpically collected. The mixture was filtered to remove solids and the volatiles were removed by distillation at reduced pressure, i^ rαxi ately 358g of product was recovered after distillation. The product contained approximately 2 weight percent boron.
The mixed alkoxylated alcx-hol-hydroquinαne borates were blended into mixed mineral oils and evaluated for antiwear performance using the Four-Ball Wear Test (ASTM D2266) for further details see U.S. Patent 4,761,482. As can be seen frαn the data in Table 1, the mixed alkoxylated _ cxhol-hy___oq_dr__r_e borates exhibit significant antiwear properties. TAKTR 1
Four--Ball Wear Test (2000 rpm, 60kg lead, 30 min, 93.33'C (200'F)
Examples Wear Scar Diameter, mm
Base oil (80% solvent 3.34 paraffiiic bright, 20% solvent paraffinic neutral mineral oils)
1% of Exanple 1 in 1.02 above base oil.
-_he mixed alloαxylated alooixsl-hydroquinone borates were blended into a ISO VG 220 Lithium hydztnystearate thickened mineral oil base grease. Dropping point evaluation using ASTM D-2265 test method was performed using each of the greases. As shown by the data in Table 2, the mixed borates of this patent information were found to sigqii-ficaπtly increase the dropping point of the grease.
Dropping Point Test. ASTM D-2265
Examples Prc p.»y- p ffl , *q C? lithium hydrxx> ~ -stearat_e thickened 210 *C (410*F) mineral oil derived grease
1% of Example 1 above base grease 252.78*C (487 *F)
2% of Example 1 above base grease 262.78'C (505*F)
3% of Example 1 above base grease 269.44'C (517 9 F)
The products of this invention exhibit very good π-ltifunctional aπtiαxidant, antiwear and hiςh-teπperature stabilizing properties especially under the severe conditions used in the performance screening tests. The prducts of this invention when used in premium quality autcmotive and industrial lubricants will significantly enhance the stability and extend the service life. The novel ccnpositions described herein are useful at low cxmceπtraticns and do not contain any potentially undesirable metals or chlorine and are ashless. These mυlt-ifunctional antioxidants can be ccra-ercially made using an economically favorable one-step, one-pot condensation process which could be readily implemented using known technology in existing equipment.
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