JPH10505107A - Dimercaptothiadiazole-mercaptan binding compounds as multifunctional additives for lubricants and fuels - Google Patents

Abstract

  (57) [Summary] It has been discovered that a combination of a dimercaptothiadiazole-mercaptan conjugate and an amine is an effective load-bearing additive for lubricants and fuels.

Description

Detailed Description of the Invention Dimercaptothiadiazole-mercaptan binding compound as a multifunctional additive for lubricants and fuels The present invention is a highly effective multifunctional antiwear / extreme pressure for lubricants and fuels It relates to a combination of a dimercaptothiadiazole-mercaptan-bonded dithio compound proven to be an additive with an amine. Dimercaptothiadiazole derivatives such as 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercaptothiadiazole disodium and 2,5-bis (t-nonyl-dithio) thiadiazole are disclosed in U.S. Pat. As described in US Pat. Nos. 661,273, 4,678,592 and 4,584,114, their antioxidant, corrosion and metal passivation properties in various lubricant applications are well known. ing. In addition, US Pat. No. 5,186,850 discloses that the incorporation of a heterocyclic dimercaptothiadiazole functionality into a succinimide structure provides multifunctional antiwear, antioxidant, and corrosion inhibiting properties in a lubricant composition. It is described as being an ashless dispersant. In addition, various reaction products of mercapto- and dimercaptothiadiazoles are available in various forms, as exemplified in U.S. Patent Nos. 4,661,273, 4,382,869 and 4,678,592. It is known to have extreme pressure / antiwear properties in lubricant formulations. It is well known that amines are used in the lubricant and detergent industries for their alkaline, surfactant and neutralizing capabilities. Amine phosphates are one of the widely used additives in industrial oils, and polyamine derived succinimides are important components in ashless dispersants for engine oils. The reaction products of dimercaptothiadiazole derived alcohols and alkenyl succinic anhydrides, and their subsequent amine reaction products, have been found to be effective antiwear / antioxidant additives for lubricants; US Pat. , 908, 144. U.S. Pat. No. 5,188,746 describes antiwear / antioxidant additives for lubricants based on dimercaptothiadiazole derivatives of acrylate and methacrylate polymers and their amine reaction products. The use of a combination of a thiadiazole-derived dithio additive with an amine derivative according to the present invention now provides very good antiwear / EP activity for lubricants and fuels, and significantly higher metal passivation / corrosion. It has been found that suppression can be obtained. The lubricants and fuel compositions according to the invention, which contain the dimercaptothiadiazole-mercaptan binding compound and the amine product in small additive concentrations, have excellent antiwear properties and good extreme pressure activity . It also appears to have antioxidant properties, cleanliness, fatigue resistance, high temperature stability and friction control. Both the thiadiazole-dithio moiety and the amine / ammonium salt moiety are believed to be the basis for the synergistic antiwear and EP properties of these new additives. All of these advantageous properties are believed to have been enhanced as a result of this novel internal synergy. It is believed that this unique concept of internal synergy is applicable to analogous structures containing (a) a thiadiazole group, (b) a dithio linking group, and (c) an amine group in the same component. The products of the present invention exhibit good stability and compatibility when used in the presence of fuels or other additives commonly used in lubricant compositions. These remarkable advantages are also expected for various synthetic and mineral oil based lubricants and fuels containing these additives, especially light distillate fuels. The compositions of the present invention and the lubricant and fuel compositions are considered novel. To our knowledge, these compositions have not previously been used in lubricating oils, greases or fuels as antiwear / extreme pressure additives. More particularly, the present invention relates to a process wherein a major part of an oil of lubricating viscosity or grease made therefrom, or a major part of a liquid hydrocarbyl or hydrocarboxy fuel, and a minor part of a dimercaptothiadiazole-mercaptan linked dithio compound. An improved lubricant or fuel comprising a multifunctional antiwear / extreme pressure additive reaction product comprising a compound with a hydrocarbylamine. Production 2,5-dimercapto-1,3,4-thiadiazole (DMTD) produced by the reaction of hydrazine with carbon disulfide is oxidatively bonded to an alkylmercaptan such as nonyl to form a thiadiazole-derived dithio compound (structure A). ) Is formed. These dithio adducts are then compounded with various amines to form a new group of additive compounds. However, Applicants do not wish to associate the additive reaction product of the present invention [Structure B], a compound of the compounded dithio adduct with various amines, to a particular structure or formula. The mercaptothiadiazole may be prepared as described above, or by any convenient method, or may be obtained as a commercial product. Any suitable such as 2,5-dimercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 4,5-dimercapto-1,2,5-thiadiazole and the like. Mercaptothiadiazole may be used. Thus, the hydrocarbyl group need not be alkyl, or is not limited to C ₉ H ₁₉ , but may be R as in the following general structure: Wherein R and R ₁ may be the same or different and are hydrogen or C ₁ to about C ₃₀ hydrocarbyl selected from alkyl, aryl, aralkyl, alkaryl, and further wherein O, S or N is Or a mixture thereof. Preferred R is C _n H _{2n + 1} , wherein n is 1 to about 30). Mercaptobenzothiadiazoles such as 6,7-dimercaptobenzo-2,1,3-thiadiazole are also considered suitable. Generally, the amines used in the present invention are aliphatic, primary, secondary or tertiary amines, preferably alkylamines or arylamines. Examples of primary amines include, but are not limited to, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, dodecylamine, triacontylamine, allylamine, 2-propylamine, cyclohexylamine, propargylamine, Isobutylamine, sec-butylamine, 2-ethylhexylamine, cyclopropylmethylamine, t-butylamine, 1,1-dimethyl-2-propynylamine, 1,1-diethyl-2-propynylamine, 1-ethynylcyclohexylamine and benzyl Amine. Examples of secondary amines include, but are not limited to, dimethylamine, diethylamine, dibutylamine, dioctylamine, ditetradecylamine, diallylamine, di-2-hexylamine, dicyclohexylamine, methylethylamine, methylcyclohexylamine, diisopropylamine , Diisopentylamine, ethylcyclohexylamine, (3-amine-propyl) alkenylamine (alkenyl groups have 16-18 carbon atoms), (3-aminopropyl) alkenylamine (alkenyl groups 18,20 and And 22 hydrogen atoms), and dihydrogenated tallow amine (eg, Armeen 2HT). Examples of tertiary amines include, but are not limited to, trimethylamine, dimethylethylamine, triethylamine, tributylamine, trioctylamine, triallylamine, triisopentylamine, tricyclohexylamine, dimethyloctylamine, n-hexadecyldimethylamine ( For example, Armeen DM16D), n-octadecyl-dimethylamine (eg, Armeen DM18D), methyl dihydrogenated tallowamine (eg, Armeen M2HT), and methyl dicocoamine (eg, Armeen M2C). Examples of arylamines include, but are not limited to, aniline 2-chloroaniline, 2-chloroaniline, 4-chloroaniline, 2-methyl-4-chloroaniline, 2,4-dichloroaniline, 3,4-dichloroaniline , 2,5-dichloro-4-nitroaniline, m-trifluoromethylaniline, isopropylaniline, p-methoxyaniline, N-methoxymethyl-2,6-diethylaniline, α-naphthylamine, N-sec-butyl-4 -T-butyl-2,6-dinitroaniline, 3-amino-2,5-dichlorobenzoic acid, N, N-dipropyl, α, α, α-trifluoro-2,6-dinitro-p-toluidine, - bromo - 3 - chloroaniline, 4 (4'-chlorophenoxy) aniline, N ^3, N ³ Jiechiru 2,4-dinitro -6-trifluoromethyl-m-phenylenediamine, p-dimethylaminoaniline, diphenylamine, p-bromoaniline, m-aminophenyl-t-butylcarbamate, o-phenylenediamine, m-phenylenediamine, 4-dimethylamino- 3,5-dimethylphenol, 4- (methylsulfonyl) -2,6-dinitro-N, N-dipropylaniline, 3,5-dinitro-N, N-dipropylsulfanylamide, N-sec-butyl-4 -T-butyl-2,6-dinitroaniline, m-toluidine, p-toluidine, m-t-butylaniline, o-anisidine, p-anisidine, dimethylaniline, o-nitroaniline, p-nitroaniline, and 4 , 4'-oxydianiline. Examples of heterocyclic amines include, but are not limited to, 3-amino-1,2,4-triazole, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, pyridine, piperidine, piperazine, Morpholine, 4,4'-dipyridyl, 8-hydroxyquinoline, 4-amino-6-t-butyl-3- (methylthio) -1,2,4-triazin-5 (4H) -one, 6-ethoxy-1 , 2-Dihydro-2,2,4-trimethylquinoline, indole, hexahydro-1H-azepine, 4-amino-5-chloro-2-phenyl-3 (2H) -pyridazinone, pyrrole, imidazolidine, isoquinoline, 2, 4-lutidine, 2-methyl-5-ethylpyridine, 2-dimethylaminopyridine, α-picoline, β-picoline, γ-picoline, Quinoline, and 4,4'-dipyridine. Examples of other possible salt-forming amino compounds include, but are not limited to, 2-chloroethyldimethylamine, diethanolaminganidin, dodecylguanidine, 3- (4-chlorophenyl) -1,1-dimethylurea, 3- (3 , 4-Dichlorophenyl) -1,1-dimethylurea, phenuron, tandex, β-aniline, methylglycine, glycinamide, aminoacetonitrile, aminoethanethiol, aminoacetic acid, diethylethanolamine, diethylenetriamine, isopropanolamine, diisopropanolamine , Triisopropanolamine, ethylenediamine, hexamethylenetetramine, hydrazine, phenothiazine, sulfanilic acid, tetraethylenepentamine, thiourea, urea, triethanolamine, triethylamine Ntetoramin a diethanol soy amine (e.g., Etomin S-12), and di deca polyoxyethylene soy amine (e.g., Etomin S-20). Examples of very suitable amines are: a) Cyclic amines: dicyclohexylamine, 1,4-diaminocyclohexane, piperidine, hexamethyleneimine, etc .; b) Heterocyclic amines: morpholine, aminopropylmorpholine (APM) , aminoethylpiperazine (AEP); c) etheramine: C ₆ -C ₁₃ alkyloxy propylamine (exons and Sherex), polyoxyalkylene amines (Texaco Jeffamine); d) diamines: exon ether diamine (DA-14, DA-17), Texaco polyoxyalkylenediamine, Akzo Juomien (Juomien C &O); e) Linear amine: ethylamine, propylamine, butylamine, pentylamine, hexylamine, dioctylamine, dicocoamine, etc. f) branched chain amines: 2-ethylhexylamine, isopropylamine, isobutylamine, diisobutylamine, bis- (2-ethylhexyl) amine, t-alkylamine (C ₁₈ -C _22), di-cocoalkyl methylamine. Mutual excesses of reagents may be used. A molar amount, a molar amount or less, or a molar amount or more of amine or dithio adduct may be used. The above reaction conditions can be largely varied depending on the specific reactants, the presence or absence of a solvent, and the like. Any suitable reaction conditions known in the art may be used. Generally, stoichiometric or equimolar ratios of the reactants are used. However, it may be used in a molar amount more or less. Anyway, the reaction conditions are not considered limiting. Generally, reaction temperatures are from ambient to about 250 ° C., or reflux, pressures are autogenous, or ambient to about 100 psi, and reaction times are from about 1 to 48 hours or more. When these dithio adducts combined with various amines are used at the additive concentration, when blended in fuels and lubricating compositions, they have excellent anti-wear properties, load-carrying activity and corrosion inhibiting properties. Is obtained. The additives specifically set forth herein provide lubricating oil or grease compositions with significant antioxidant, load and corrosion inhibiting properties to the oil or grease, and operate with the oil in the crankcase. Used in amounts that reduce engine friction. It can be used at a concentration of 0.001 to 10% by weight based on the total weight of the composition. 0. A concentration of 1 to 3% by weight is preferred. These materials are also considered suitable for liquid hydrocarbyl or alcohol or mixed hydrocarbyl / alcohol fuel compositions. These are commonly used in amounts of 50-500 pounds per 1000 barrels of fuel. The additive improves the antiwear and friction reducing properties of various oleaginous materials, such as hydrocarbyl lubricating media, including liquid oils in the form of mineral or synthetic oils, or greases in which the oils are used as vehicles. Have the ability to Generally, the mineral oils or grease vehicles of the paraffinic and naphthenic and mixtures thereof used as lubricants may be of any suitable lubricating viscosity, for example, 6 mm ² / s at 38 ° C. (100 ° F.). About 45 SSU) to 1200 mm ² / s at 38 ° C (about 6000 SSU at 100 ° F), preferably 7.5 (about 50) to 62 mm ² / s (about 250 SSU) at 99 ° C (210 ° F). . These oils having a viscosity index of about 95 are preferred. The average molecular weight of these oils is between 250 and 800. If the lubricant is used in the form of a grease, the lubricating oil must be sufficient to balance the entire grease composition after being occupied by the desired amount of thickener and other additive components to be included in the grease formulation. It is generally used in large amounts. Various materials may be used as thickening or gelling agents. These include any of the common metal salts or soaps, which are dispersed in the lubricating vehicle in a grease forming amount that provides the desired consistency to the resulting grease composition. Other thickeners that can be used in grease formulations comprise non-soap thickeners such as surface modified clays and silicas, aryl ureas, calcium complexes and the like. In general, grease thickeners are used that do not melt and dissolve when used at the required temperature in a particular environment; however, in all other respects, carbonizing Any substance commonly used for thickening or gelling a hydrogen liquid can be used to make the grease of the present invention. When synthetic oils or synthetic oils used as lubricants or vehicles for greases are more desirable than mineral oils or combinations thereof, various compounds of this type are conveniently used. Common synthetic oils include, but are not limited to, polyisobutylene, polybutene, hydrogenated polydecene, polypropylene glycol, polyethylene glycol, trimethylolpropane ester, neopentyl and pentaerythritol esters, di (2-ethylhexyl) sebacate, di- (2-ethylhexyl) adipate, dibutyl phthalate, fluorocarbon, silicate ester, silane, ester of phosphorus-containing acid, liquid urea, ferrocene derivative, hydrogenated synthetic oil, chain-type polyphenyl, siloxane and silicone (polysiloxane), butyl-substituted bis Alkyl-substituted diphenyl ethers represented by (p-phenoxyphenyl) ether and phenoxyphenyl ether are included. However, it goes without saying that the composition of the present invention may contain other substances. For example, corrosion inhibitors such as metal phenate sulfonates, high molecular weight succinimides, non-metal or metal phosphorodithioates, extreme pressure agents and the like can be used. These substances do not impair the usefulness of the compositions according to the invention and serve to confer the customary properties to the individual compositions in which they are mixed. The following examples are intended to illustrate the invention, but not to limit the scope of the invention. Example 1 Approximately 95 g of 2,5-bis (t-nonyl-dithio) thiadiazole (commercially available from Amoco Chemical under the trademark Amoco 158 or Mobilad C-610 under the trademark trademark Mobilad C-610). ) And 5 g of isodecyloxypropylamine (commercially available from Shellex Chemical Company under the trademark ADGEN 180) were compounded in a mixer at 80 ° C for 2 hours. After rapid filtration, about 99.5 g of a tan liquid was recovered as the desired compounded product. Example 2 About 90 g of 2,5-bis (t-nonyl-dithio) thiadiazole and 10 g of isodecyloxypropylamine were blended in a mixer at 80 ° C. for 2 hours. After rapid filtration, about 99.2 g of a tan liquid was recovered as the desired compounded product. Example 3 Example 2 except that C _18-22 t-alkyl primary amine (commercially available from Rohm Haas Chemical Company under the trademark Primen JM-T) was used in place of isodecyloxypropylamine. The reaction procedure was followed. Example 4 The reaction procedure of Example 1 was followed except that oleyl 1,3-diaminopropane (commercially available from Akzo Chemical Company under the trademark DuoMine 0) was used in place of isodecyloxypropylamine. . The products of Evaluation Examples 2, 3 and 4 were blended in industrial oils and evaluated for antiwear performance using the Four-Ball test (Table 1). As is evident from the above wear test results, the product shows considerable antiwear activity. The products of the Examples were mixed into a fully formulated engine oil: the products of Example 1 were evaluated for load-bearing capacity in a Four Ball EP test (Table 2); the products of Examples 1 and 2 were FZG gear testers (Table 3). In the Four Ball wear test, three fixed balls are placed in a lubricant cup, a lubricant containing the test compound is added thereto, and a fourth ball is used on a device that can be used to rotate the ball at a known speed and load. Place with the chuck attached. The tests were performed using 1/2100 stainless steel balls of 52100 steel for 30 minutes under a 60/40 kg load at 1500 and 1800 rpm and 93 ° C (200 ° F). For further information regarding this test, reference may be made to test method ASTM D2266 and / or U.S. Pat. No. 4,761,482. The Copper Strip Corrosion Test (ASTM D-130) measures the tendency of products to corrode copper, for example by including sulfur groups. For more details, reference may be made to the ASTM standards for petroleum products and lubricants issued annually by the American Society for Testing and Materials. The Four-Ball EP test (ASTM D-2783) measures the extreme pressure or load bearing properties of a lubricant by measuring the load and wear index (LWI) and the point of adhesion. The test ball is rotated under load at the tetrahedral position of the top of the three fixed balls soaked in the lubricant. LWI was calculated by measuring the scratches of three fixed balls, and the adhesion is the load at which the four balls adhered together within 10 seconds. The last non-seize load is the final load at which the measured flaw diameter is 5% or less of the correction line at that load. The correction line is a logarithmic plot of the wound diameter (mm) and load (kg) coordinates obtained under dynamic conditions. The higher the LWI value, the better. See U.S. Patent No. 4,965,002 and ASTM D-2783. FZG gear test (DIN-51.354). In this test, the weight of an immersion lubricated gear is measured and operated in test gear oil at a constant speed and a constant initial oil temperature (90 ° C.). Increasing the load on the teeth. After each loading stage, the weight change is measured and recorded. The results are shown in Table 3. The higher the rejection grade, the better. The lower the abrasion value, the better the weight change and / or visual condition. Details are described in CEC method L-07-A-71. As mentioned above, the products of the present invention are evidenced by improved wear properties and load bearing from stage 7 to stages 10 to 12 on the FZG tester and a rating of LWI in the Four Ball EP test. Thus, it exhibits very good anti-wear properties and extreme pressure activity. Furthermore, the products of the present invention show excellent corrosion inhibition. The use of bis (alkyl-dithio) thiadiazole and amine additive formulations in rare quality industrial and engine lubricants significantly increases stability, improves load carrying capacity, reduces wear, and extends useful life. Become. These additive formulations have the potential to make gasoline and diesel fuels advantageous by improving their antioxidant, antiwear and corrosion inhibiting properties. These novel compositions according to the invention are effective at low concentrations and do not contain potentially unwanted metals or phosphorus. These dual-function antiwear / EP-antioxidants can be readily manufactured commercially.

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Claims (1)

[Claims] 1. A non-phosphorus, multi-part, non-phosphorus-rich mixture of a lubricating viscosity oil or grease produced therefrom, or a liquid hydrocarbyl fuel, and a small part of a dimercaptothiadiazole-mercaptan-bonded dithio compound and hydrocarbylamine. An improved lubricant (or fuel) composition comprising a functional antioxidant, load bearing, antiwear / extreme pressure and corrosion inhibitor additive reaction product, wherein the reaction is at ambient temperature to about 250 ° C, And at ambient pressure to about 100 psi, or autogenous pressure, about 1 to about 48 hours, sufficient to obtain the desired additive reaction product, in equimolar to greater than or less than 1 mole molar ratio of reactants. The above composition, which is performed. 2. The additive reaction product has a structural formula Wherein R and R ₁ may be the same or different and are hydrogen or C ₁ to about C ₃₀ hydrocarbyl selected from alkyl, aryl, alkaryl, aralkyl, and further O, S, N Or a mixture thereof) of a thiadiazole-derived dithio compound and hydrocarbylamine at ambient temperature to about 250 ° C. and ambient pressure to about 100 psi, or autogenous pressure, at the desired additive reaction. The composition of claim 1, wherein the composition is generally prepared by reacting the reactants at a molar ratio of from equimolar to greater than or less than 1 mole for about 1 to about 48 hours sufficient to obtain the product. 3. The composition according to claim 1, wherein the dithio compound is 2,5-bis (t-nonyl-dithio) thiadiazole and the amine is isodecyloxypropylamine. 4. The oil of lubricating viscosity is selected from (1) mineral oil, (2) synthetic oil, or (3) a mixture of mineral oil and synthetic oil, or (4) (1), (2) or (3) The composition of claim 1 which is a grease made from any one of the preceding claims. 5. The composition of claim 4, wherein the lubricant contains 0.001 to 10% by weight of the additive reaction product based on the total weight of the composition. 6. The composition according to claim 4, wherein the lubricant is a mineral oil. 7. The composition according to claim 4, wherein the lubricant is a synthetic oil. 8. The composition according to claim 1, wherein the fuel is selected from liquid hydrocarbyl, hydrocarboxy or alcohol fuel, or a mixture of hydrocarbyl and alcohol fuel. 9. 9. The composition of claim 8, wherein the fuel contains 23-227 kg of the additive per 159000 liters of fuel. 10. 9. The composition of claim 8, wherein the fuel is a distillate fuel. 11. It consists of a dimercaptothiadiazole-mercaptan-bonded dithio compound and a hydrocarbylamine which impart non-phosphorus, multifunctional load-bearing and corrosion-inhibiting properties to an oil of lubricating viscosity or a grease produced therefrom. , Lubricant fuel additive reaction products. 12. Structural formula Wherein R and R ₁ may be the same or different and are hydrogen or C ₁ to about C ₃₀ hydrocarbyl selected from alkyl, aryl, alkaryl, aralkyl, and further O, S, N Or a mixture thereof) of a thiadiazole-derived dithio compound and hydrocarbylamine at ambient temperature to about 250 ° C. and ambient pressure to about 100 psi, or autogenous pressure, at the desired additive reaction. 12. The additive product of claim 11, wherein the additive product is prepared by reacting at a molar ratio of reactants of from equimolar to greater than or less than 1 mole for about 1 to about 48 hours sufficient to obtain the product. 13. The additive according to claim 11, wherein the reactants are 2,5-bis (t-nonyl-dithio) thiadiazole and isodecyloxypropylamine.