MX2008005431A - High performance lubricant additives - Google Patents

Abstract

A lubricant additive produced by the process comprising mixing an organophosphate and an organofluorine compound and reacting the organophosphate and the organofluorine compound to produce a reaction mixture comprising the lubricant additive. Also, a lubricant produced by the process comprising forming a reaction mixture by reacting an organophosphate and an organofluorine and adding at least a portion of the reaction mixture to a lubricant base.

Description

ADDITIVES FOR HIGH PERFORMANCE LUBRICANTS TECHNICAL FIELD The present application relates generally to additives for lubricants and, more particularly, to additives for high-performance lubricants that increase the desirable lubricating properties of the lubricant.

BACKGROUND OF THE INVENTION Lubricants comprise a variety of compounds selected by desirable characteristics such as anti-wear and anti-friction properties. Common commercial lubricants are compositions containing a lubricant base such as a hydrocarbon oil or grease, to which numerous lubricant additives selected for additional desirable properties are added. Lubricant additives can increase lubricity of the lubricant base and / or can provide anti-wear characteristics or other desirable characteristics.

Lubricants are used in huge quantities. For example, more than four trillion quarts of crankcase oil are used in the United States every year. However, many lubricants currently in use also have undesirable characteristics. Crankshaft crankcase oils currently available generally include zinc alkyldithiophosphate (ZDDP) anti-wear additive, which contains phosphorus and sulfur. Phosphorus and sulfur poison catalytic converters causing increased automotive emissions. It is expected that the EPA will eventually order the total elimination of ZDDP or allow only extremely low levels of ZDDP in oil for crankcase crankshafts. However, no acceptable anti-wear additive to replace ZDDP in motor oils is currently available.

In addition, the lubricant bases used in conventional lubricants usually have additives for lubricants added thereto to improve lubricity. Many of these lubricant additives do not provide sufficient additional lubricity and / or possess additional undesirable characteristics.

Accordingly, it is an object of the present invention to provide non-aggressive environmentally friendly anti-wear additives for lubricants, wherein the amounts of phosphorus and sulfur in the anti-wear additive are significantly reduced and approach zero. Another objective of the present invention is to produce compounds with desirable anti-wear and antifriction characteristics.

BRIEF DESCRIPTION OF THE INVENTION The embodiments of the invention comprise methods for preparing additives for lubricants and lubricants by reacting together organophosphates such as zinc dialkyl thiophosphate (ZDDP) and organofluor compounds such as polytetrafluoroethylene (PTFE). The PTFE used with embodiments of the present invention comprises more than 40 carbon atoms. In one embodiment, ZDDP and PTFE are reacted together at about -20 ° C to about 150 ° C. In a preferred embodiment, ZDDP and PTFE are reacted together at a temperature of about 60 ° C to about 150 ° C. The reaction is allowed to continue for about 20 minutes to about 24 hours. Both supernatants and precipitates formed during the reaction can be used as additives for lubricants. These lubricant additives can be added to lubricants such as oils, greases, fluids for automatic transmission, fluids for crankcase crankshafts, engine oils, hydraulic oils and gear oils. In certain embodiments, organophosphate and organofluor compounds can be added to a lubricant base and then allowed to react under specific conditions.

Other embodiments of the present invention react a mixture of powdered and chewed metal halides with an organophosphate such as ZDDP and an organofluor such as PTFE to form an additive for lubricants or lubricant. In still other embodiments, other forms of metal halides may be used that are not powdered and / or chewed. The metal halide used is metal fluoride in a preferred embodiment of the invention. In a preferred embodiment, the metal fluoride, ZDDP and PTFE are reacted together at about -20 ° C to about 150 ° C to form a lubricant additive. The lubricant additive is then added to a lubricant. The lubricants to which the lubricant additive is added are preferably fully formulated GF4 engine oils without ZDDP. However, other lubricants such as those listed above may be used.

The foregoing has delineated very broadly the characteristics and technical advantages of the present invention so that the detailed description of the following invention can be better understood. The additional features and advantages of the invention will be described hereinafter which form the object of the claims of the present invention. It should be appreciated that the specific conception and embodiment described can easily be used as a basis for modifying or designing other structures to accomplish the same purposes of the present invention. It should also be noted that these equivalent constructions do not depart from the invention as shown in the appended claims. The new characteristics that are believed to be the feature of the invention, both in terms of its organization and the method of operation, together with additional objectives and advantages, will be better understood from the following description when considered in relation to the accompanying figures. It should be expressly understood, however, that each of the figures is provided for the purpose of illustration and description only and is not intended as a definition of the limits of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawing, in which: Figure 1 is a table of possible organophosphate formulas used with certain embodiments of the present invention.

Figures 2A-D show various organophosphate structures used with certain embodiments of the present invention.

Figure 3 shows PTFE structures used with certain embodiments of the present invention.

Figures 4A and 4B show reaction products of certain embodiments of the present invention.

Figures 5A-5C show graphs illustrating the results of the ASTM D2596 4-ball weld loading experiments in which lubricating grease containing various amounts of ZDDP, PTFE, catalyst and / or molybdenum disulfide were present.

Figures 6A and 6B are graphs summarizing the results of ASTM D2596 4-ball weld loading experiments used to generate the cube graphs of Figures 5A-5C.

Figure 7 is a graph that summarizes the results of a cylinder block test for several lubricants.

Figure 8 is a graph of experimental results of a block-on-cylinder test comparing various fat compositions.

Figure 9 shows three-dimensional predictions of wear dimensions based on experimental results of cylinder block tests comparing fat compositions.

Figure 10 shows the results of differential scanning calorimetry (DSC) tests to determine the decomposition temperatures of ZDDP and Figure 1 1 shows wear volume test results for engine oils from a ball-over-cylinder test.

DETAILED DESCRIPTION OF THE INVENTION The embodiments of the present invention provide additives for improved high performance lubricants and lubricants that provide improved wear protection, lower friction coefficients and lower cohesive energy surfaces. Additives for lubricants provided according to the embodiments of the present invention can be added to lubricants such as greases, oils for crankcase, hydrocarbon solvents, etc. The embodiments of the present invention generally react together with organophosphate compounds and organofluorine compounds, with or without metal halides and / or molybdenum disulfide, to produce lubricant additives.

Figure 1 is a table showing several of the organophosphate compounds that can be used with embodiments of the present invention. Generally, dithiophosphates and ammonium and amine salts of monothiophosphates and dithiophosphates can be used. Meta organophosphates and organothiophosphates such as zinc dialkyldithiophosphate (ZDDP) are encompassed by the term "organophosphate" for the purposes of this disclosure. Other organophosphates listed in Figure 1 include neutral ZDDP (primary), neutral ZDDP (secondary), basic ZDDP, (RS) 3P (s) wherein R > CH3, (RO) (R 'S) P (O) SZn ", (RO) 2 (RS) PS where R> CH3, P (S) (S) Zn ", (RO) 2P (S) (SR), R (R'S) 2PS where R = CH3 and R '> CH3, (RO) 3PS where R = CH3 and R '= alkyl, MeP (S) Cl2, (RO) 2 (S) PSP (S) (OR) 2, P (S) (SH), (RO) (R) 'S) P (O) SZn \ SPH (OCH3), wherein R = any alkyl and R' = any alkyl, and combinations thereof. The chemical structures of representative compounds of Figure 1 and additional organophosphate compounds that can be used with the invention are shown in Figures 2A-2C. In certain embodiments of the present invention, organophosphates not shown in Figures 2A-2C can be used.

The organophosphate ZDDP is used in preferred embodiments of the present invention. Modes using ZDDP, alone or in combination with other organophosphates, can use ZDDP in one or more portions. Preferably, the ZDDP used is the neutral or basic portion. Some of the ZDDP portions are shown in Figure 2A as structures 1 and 5. In a preferred embodiment, the total ZDDP alkyl groups are about 1-20 carbon atoms. The alkyl groups of the ZDDP can take various forms known to those skilled in the art such as branched or straight chain primary, secondary or tertiary alkyl groups.

Additional organophosphate structures which may be useful with embodiments of the present invention are shown in Figure 2D. The organophosphate structures specifically described herein are representative structures and are in no way designed to limit the embodiments of the present invention to those structures. Many embodiments of the present invention utilize organophosphate compounds not specifically shown.

A variety of organofluor compounds can be used with the present invention. Polytetrafluoroethylene (PTFE) and its derivatives are particularly suitable for use with embodiments of the present invention. The PTFE structures are shown in Figure 3. Other organofluor compounds which are usable include, but are not limited to, fluoroalkyl carboxylic acids, fluoroaryl carboxylic acids, fluoroalkylaryl carboxylic acids and the like; compositions comprising fluoroalkyl sulfonic acids, fluoroaryl sulfonic acids or fluoroalkylaryl sulfonic acids, and the like, and their derivatives, such as alkyl and fluoroalkyl esters and alkyl and fluoroalkyl alcohols and alkyl or fluoroalkyl amides. Particularly preferred compositions are those described above having more than one functional group, these compositions include any combination of two or more functional groups including carboxylic acids, sulfonic acids, esters, alcohols, amines and amides, and mixtures thereof. The organofluor compounds can be partially fluorinated or perfluorinated. Certain of these organofluor compounds can catalyze the decomposition of organophosphate materials with which they are mixed at a lower temperature than without these materials present. Also, these compositions can react with metal fluorides, such as FeF3 and TiF3, ZrF4, A1F3 and the like. In general, the organofluor materials may be of high, low or moderate molecular weight.

Certain embodiments of the present invention comprise methods for preparing additives for lubricants by reacting together zinc dialkyldithiophosphate (ZDDP) and polytetrafluoroethylene (PTFE), wherein the PTFE comprises more than 40 carbon atoms. PTFE molecules comprising more than 40 carbon atoms are particularly suitable for use with embodiments of the present invention, since this type of PTFE is generally insoluble in mineral oils and other lubricants. A preferred embodiment of the invention uses PTFE with a composition of between 40 and 6,000 carbon atoms. A reaction between PTFE and ZDDP according to embodiments of the present invention can take place outside a lubricating environment, producing a reaction mixture. The reaction mixture or components thereof can then be added to a base lubricant as a lubricant additive to improve various characteristics of the base lubricant. As an alternative, certain embodiments of the present invention comprise adding a mixture of PTFE and ZDDP to a base lubricant. The reaction between PTFE and ZDDP then takes place in the lubricating environment, either before or during use in a desired application. In preferred embodiments, the base lubricant comprises about 0.01 weight percent phosphorus to about 0.1 weight percent phosphorus.

The organofluor compounds such as PTFE compounds used in embodiments of the present invention may be of various molecular weights and of various particle sizes. PTFE molecular weights of about 2,500 to about 300,000 are used in certain embodiments of the present invention. The PTFE particle sizes in certain embodiments of the present invention range from about 50 nm to about 10 μm. In preferred embodiments, the PTFE used is added as a solid in the form of particles with a diameter of about 50-500 nm. Figure I B shows exemplary molecular structures of PTFE that can be used in certain embodiments of the present invention.

An electron beam irradiated PTFE is also used in the preferred embodiments. The irradiated PTFE comprises additional active end groups formed by carrying out the irradiation process in an air environment. During the process, the long chain PTFE molecules are cut to form shorter chain molecules with polar end groups such as carboxyl groups. The PTFE molecules loaded with carboxyl groups present can be attracted to metal surfaces, as explained in SAE Publication No. 952475 entitled "Mechanism Studies with Special Boundary Lubricant Chemistry" by Shaub et al., And in SAE Publication No. 941983 entitled "Engine Durability, Emissions and Fuel Economy Studies with Special Boundary Lubricant Chemistry" by Shaub et al., whose contents are incorporated herein by reference. Combined irradiated PTFE with an organophosphate such as, for example, ZDDP, can improve the decomposition rate of ZDDP and form reaction products that are useful as additives for high performance lubricants.

In certain embodiments of the present invention, ZDDP and PTFE are reacted together by adding PTFE in solid form to a suspension of ZDDP under specified conditions. In a preferred embodiment, the PTFE used is irradiated PTFE, such as Nanoflon ™ powder manufactured by Shamrock Technologies, Inc., and NF 1 A manufactured by DuPont. In other embodiments, SLA-1612 (a dispersion of PTFE in oil) manufactured by Acheson Industries, Inc. is used. However, various commercial and non-commercial PTFE compounds may also be used in embodiments of the present invention. Also in a preferred embodiment, the ZDDP is contained in a suspension comprising 68% of ZDDP by weight in paraffin oil or hydrocarbons. However, ZDDP can be suspended in other liquid phase compounds known to those of ordinary skill in the art.

Once combined, the ZDDP and PTFE are reacted by cooking at a temperature of about -20 ° C to about 150 ° C. In a preferred embodiment, the reagent mixture is reacted at a temperature of about 60 ° C to about 150 ° C. The reaction is allowed to continue for about 20 minutes to about 24 hours. Generally, upon reducing the temperature in embodiments of the invention, the duration of the reaction is increased. Several additional reaction parameters can be used, such as carrying out the reaction under certain gases such as air, oxygen, nitrogen or noble gases, or by stirring the reagents to promote the progress of the reaction, or by applying ultrasonication to carry out reactions. Faster. Both supernatants and precipitates formed during a reaction can be used as additives for lubricants in certain embodiments of the present invention. Supernatants and precipitates can be separated using standard techniques such as filtration or centrifugation known to those skilled in the art.

In a preferred embodiment, one atteat a reaction as described above is to produce two products. One is a clear decanted liquid comprising neutral ZDDP, fluorinated ZDDP and / or a PTFE complex having ZDDP groups, phosphate and thiophosphate attached. The first product can be used for oils as a high performance additive low in phosphorus content and in fats as a high performance additive. The second product comprising settled or centrifuged solids comprises mainly PTFE and complexes of PTFE with ZDDP, phosphates and thiophosphates, and can be used as an additive for fats. Both reaction products are believed to have affinity for metal surfaces. When used (or formed, as described below) in a lubricant composition, the reaction products are bonded to, or concentrated on, the metal surface, providing protection against wear and friction. Figures 4A and 4B show PTFE / ZDDP complexes which are possible reaction products that can be formed in certain embodiments of the present invention. However, these are only an exemplary product and additional structures can be formed in these and other embodiments of the present invention. Although ZDDP and PTFE are a focus of the above description, it is expected that other organophosphates and organofluoro compounds will produce similar reaction products usable as high performance additives.

In certain embodiments, one or more compounds with reactivity, thereby accelerating or carrying out a reaction, may be added to a reaction mixture of ZDDP and PTFE. These reactive agents can accelerate the reaction with ZDDP, PTFE or both, or other materials with these compositions, to give new additives for lubricants. Metal halides such as ferric fluoride are reactive materials used in preferred embodiments of the present invention. The metal halides used with certain embodiments of the present invention can be, for example, aluminum trifluoride, zirconium tetrafluoride, titanium trifluoride, titanium tetrafluoride and combinations thereof. In other embodiments, other transition metal halides are used, such as, for example, difluoride and chromium trifluoride, difluoride and manganese trifluoride, nickel difluoride, stannous difluoride and tetrafluoride, and combinations thereof. Ferric fluoride can be produced according to a process described in the patent application of E.U.A. Copendent Serial No. 10 / 662,992 filed September 1, 2003, the contents of which are incorporated herein by reference. In embodiments that react metal halides with ZDDP and PTFE, the resulting reaction mixtures can comprise both solid and liquid phase components. A liquid phase product comprising complexes of fluorinated ZDDP and PTFE with linked ZDDP, phosphate and thiophosphate groups can be used for both oils and fats and a low phosphorus and high yield additive respectively. The solid phase product comprising settled or centrifuged solids comprises mainly PTFE and unreacted ferric fluoride and can be used as an additive for fats. Both reaction products are believed to have affinity for metal surfaces. The solid phase components can be similar to those illustrated in Figures 4A and 4B. Additional compounds can result from these reactions that may have minor lubricant characteristics.

Irradiated PTFE is particularly suitable for use with reaction mixtures comprising organophosphates and metal halides, since it interacts strongly with these compounds resulting in reaction products that can be used as additives for high performance lubricants. The perfluoroalkylcarboxylic acids of medium to high molecular weight, or the fluorinated alkyl, aryl or alkylarylcarboxylic acids are also substantially particularly suitable for use with embodiments of the present invention. Organofluoro compounds such as fluoroalkyl, fluoroalkylaryl, fluoroaryl and fluoroarylalkyl alcohols and amines of all molecular weights are also useful with embodiments of the present invention. Particularly preferred compositions are those described above having more than one functional group, such as a composition comprising any combination of two or more functional groups comprising carboxylic acids, sulfonic acids, esters, alcohols, amines and amides and mixtures thereof . In certain embodiments of the present invention, organofluor compounds used are soluble in neutral oils at room temperature.

In a preferred embodiment of the present invention, an additive or lubricant or additives produced as described above are mixed as a motor oil completely formulated without ZDDP. The term "fully formulated oil" as used herein to illustrate certain embodiments of the present invention are motor oils that include additives, but not ZDDP. In certain embodiments, the fully formulated oil may be, for example, a GF4 oil with an additive package comprising standard additives, such as dispersants, detergents and antioxidants, but without ZDDP. A reaction between ZDDP and PTFE can then be obtained before or during the desired use of the lubricant.

In certain embodiments of the present invention, a reaction between an organophosphate and an organofluoride further comprises the interaction of the reactants with molybdenum disulfide as a reactant or catalyst. In still other embodiments, a metal halide composition is added to the mixture to further increase the lubricating properties of the resulting reaction products. As shown below in the experimental results of Figures 5A-5C, molybdenum disulfide can increase the lubricating properties of lubricant additives by forming possible disulfide and molybdenum complexes with reaction products formed by organophosphate and organofluoride reagents. However, other mechanisms may be responsible for the synergistic effect of molybdenum disulfide as illustrated in Figures 5A-5C. The synergistic effects occur, for example, when a first compound only produces a first effect and a second compound only produces a second effect, but the compounds combined together produce an effect that is greater than the sum of the effects of the compounds when used alone Following are the results of a series of experiments that were carried out to determine the properties of lubricants and lubricant additives produced according to embodiments of the present invention. 4 Ball Welding Test (ASTM D2596) This experimental protocol measures the extreme pressure properties of lubricants such as fats. A first ball that rotates at 1, 800 rpm is put in sliding contact with three other balls. The contact force between the first ball and the other three balls is adjustable, and the complete assembly of four balls is immersed in the lubricant being tested. During this test, the contact force between the balls, or test load, is raised in stages until the balls are welded together at a point known as the weld load. A higher weld load is more desirable and is generally a feature of compounds with better lubricating properties. Figures 5A-5C show graphs illustrating the results of experiments in which lubricating grease containing various amounts of ZDDP, PTFE, catalyst and / or molybdenum disulfide were present. The results shown in Figures 5A-5C are weld load values based on an experimental design in which various fat chemistries were tested and the data was used to predict the result of the listed chemicals. The actual data used for the predicted values are listed in Figure 6A and 6B.

Figure 5A is a graph showing the weld load for fats comprising varying amounts of ZDDP and PTFE with 0.5 weight percent molybdenum disulfide. At a concentration of 2.0 percent by weight of ZDDP and PTFE, respectively, with minimum ferric fluoride catalyst present, the composition charge was determined to be about 642 kg compared to a base weld load of about 197 kg.

The compositions tested to generate the results tested in Figure 5B comprised varying amounts of ZDDP and PTFE together with 1.25 weight percent molybdenum disulfide. Here, the weld load was determined to be about 719 kg at a concentration of 2.0 percent by weight of ZDDP and PTFE with a minimum ferric fluoride catalyst present. The base solder charge with 1.25 weight percent of the molybdenum disulfide is about 2.58 kg.

The compositions tested to generate the results shown in Figure 5C comprised varying amounts of ZDDP and PTFE together with 2.0 weight percent molybdenum disulfide. Ferric fluoride catalyst (0.2 weight percent) was present. In other embodiments, ferric fluoride at a concentration of from about 0.1 to about 1.0 percent by weight can be used. At a concentration of 2.0 percent by weight of ZDDP and PTFE, respectively, the weld filler for the composition was determined to be approximately 796 kg with the minimum ferric fluoride catalyst present. The base solder charge with 2.0 weight percent molybdenum disulfide is about 3 19 kg.

The results of the experiments shown in the graphs of Figures 5A-5C indicate that increasing the concentration of molybdenum disulfide provides an increase in the lubricating properties of the fat formulation, although the increase is quite modest compared to the effect of adding ZDDP and PTFE to fat. The graphs show that a synergistic interaction between ZDDP and PTFE is present, since ZDDP and PTF by themselves do not provide significant protection against extreme pressures. The addition of 2.0 percent by weight of ZDDP and PTFE to fat more than doubled the weld load for fat composition compared to base grease and molybdenum disulfide alone. The addition of ferric fluoride catalyst also produced a synergistic effect with PTFE when PTFE was added in the absence of ZDDP to the fat / molybdenum disulfide composition. This effect was greater at higher molybdenum disulfide concentrations. A minor synergistic effect with ferric fluoride catalyst was also present with molybdenum fat / disulfide compositions containing ZDDP in the absence of PTFE.

Figure 6A is a bar graph summarizing the results of the experiments used to generate the cube graphs of the figures 5A-5C. The highest weld filler obtained (796 kg) was with a fat composition of 2.0 weight percent of ZDDP, PTFE and molybdenum disulfide together with 0.2 weight percent ferric fluoride catalyst. Figure 6B is a legend corresponding to the horizontal axis markings of Figure 6A. The results show that a welding load of 620 kg can be obtained only with 2 percent ZDDP and 2 percent PTFE and without other ingredients, indicating a strong synergy between PTFE and ZDDP.

Block Testing on Cylinder (Modified Timken Testing) Figures 7-9 show the results of block-on-cylinder tests that model the wear life properties of lubricants under the rotational movement of a ring against a block. A cylinder, with 4 grams of test lubricant applied evenly on its outer surface, is rotated at 700 rpm against a test block. The test block rises from under the cylinder and makes contact with the cylinder with a predetermined load applied by a pneumatic system. The width of the wear mark on the block is used as a measure of wear performance. The coefficient of friction and test temperature are determined as part of the test. The tests were carried out for a total of one hour at a load of 20 kg for 42,000 cycles.

Figure 7 shows that lubricating compositions comprising irradiated PTFE performed better than non-irradiated PTFE. A base grease composition showed the highest coefficient of friction (> 0.35) and the highest temperature at the conclusion of the test. A composition comprising base grease, 2.0 percent by weight of ZDDP, 2.0 percent by weight of unirradiated PTFE and 2.0 percent by weight of powdered ferric fluoride catalyst performed significantly better, with a coefficient of friction of about 0.26 and a test temperature of around 15 ° C. The test composition comprising base grease, 2.0 weight percent ZDDP, 2.0 weight percent irradiated PTFE and 2.0 weight percent ferric fluoride catalyst powder had the best performance, with a coefficient of friction around of 0.22 and a test temperature of around 10 ° C. In the absence of additives, the contact temperature increases continuously and no protective film is formed on the surface. The graph of the composition comprising irradiated PTFE demonstrates the formation of a protective tribo film on the surface and a corresponding drop in the temperature of the test block. Optical micrographs (not shown) indicate that the fat composition with irradiated PTFE produces the narrowest and shallowest wear mark of the three tested compositions. The results summarized in Figure 7 indicate that compositions comprising irradiated PTFE perform better than compositions comprising a non-irradiated PTFE, even with a lower ZDDP content.

Figure 8 is a graph of experimental results of a block-on-cylinder test comparing several fat compositions, the graph shows the coefficients of friction calculated for various experimental compounds. A base grease composition with 2.0 percent by weight of ZDDP produced a wear mark width of 0.74 mm. A fat composition comprising base grease, 0.5 weight percent ZDDP, 2.0 weight percent PTFE, 2.0 weight percent molybdenum disulfide, and 0.2 weight percent Ferric Fluoride Catalyst yielded a brand width of wear of 0.676 mm. The best result was obtained with a base fat grease composition, 2.0 percent by weight of ZDDP, 2.0 percent by weight of PTFE, 0.5 percent by weight of molybdenum disulfide and 0.2 percent by weight of ferric fluoride catalyst. , which produced a wear mark of 0.3949 mm. This data set indicates a synergistic interaction between ZDDP, PTFE and ferric fluoride that produces low friction coefficients and the best wear results.

Figure 9 shows three-dimensional predictions of dimensions of wear marks with experimental results from block-to-cylinder tests comparing fat compositions. The load used was 30 kg in these tests. The wear mark of a fat composition comprising 0.5 weight percent of ZDDP was determined to be 0.456 mm, while the same fat composition comprising an increased amount of 2.0 weight percent of ZDDP produced a mark of much smaller wear of 0.365 mm. This beneficial behavior of ZDDP is maintained in various concentrations of molybdenum disulfide. For both compositions, increasingly higher concentrations of molybdenum disulfide also increased the width of the wear mark. For example, at a concentration of 2.0 percent by weight of ZDDP, the width of the wear mark was 1 .3 19 mm when the composition comprised 2.0 percent by weight of molybdenum disulfide, and only 1,074 mm with 0.5 percent by weight. 100 weight percent molybdenum disulfide. The results indicate that the molybdenum disulfide is antagonistic to the wear performance at low loads, resulting in an increase in wear.

Figure 10 shows the results of barrel or differential calorimetry (DSC) tests to determine the decomposition temperatures of ZDDP. The DSC tests were carried out at -30 ° C to 250 ° C at a ramp speed of 1 ° C / minute under nitrogen. The samples were heated in hermetically sealed aluminum pans. ZDDP only decomposes at approximately 18 1 ° C. In the presence of PTFE (irradiated Nanoflon ™ powder), the ZDDP decomposes at about 166 ° C, and decomposes at 155 ° C in the presence of PTFE and ferric fluoride catalyst. ZDDP and PTFE were mixed in a 1: 1 ratio, and ZDDP / PTFE / ferric fluoride were mixed in a 2: 2: 1 ratio. The DSC results indicate that in the presence of PTFE the decomposition temperature of ZDDP is reduced by about 15 ° C. In the presence of both PTFE and ferric fluoride, the decomposition temperature is reduced by approximately 26 ° C.

Ball Test on Cylinder Figure 1 1 shows the wear volume test results for engine oils. The test used is a ball-on-cylinder test that evaluates the wear prevention properties of the lubricants. A steel cylinder (67 HRC) is rotated at 700 rpm against a tungsten carbide ball (78 HRC) which is loaded with a lever arm to apply a load of 30 kg. Fifty microliters of test lubricant are applied evenly across the outer surface of the cylinder at the point of contact with the ball. The wear mark depth and wear volume are calculated at the conclusion of the test. The lubricant compositions were prepared as follows. ZDDP and PTFE in a 1: 1 ratio were baked in air at 150 ° C for 20 minutes and then centrifuged to remove all solids. A measured amount of the supernatant liquid was added to a Chevron 100N base oil to produce less than 0.05 weight percent phosphorus for the lubricant composition. The graph shows that the wear volume for this composition was 0.859 mm compared to the wear volume of 0.136 mm3 for a fully formulated commercial GF4 oil comprising 750 ppm phosphorus and 80 ppm molybdenum disulfide. The results indicate that the synergistic effects of a ZDDP / PTFE composition are effective in formulations designed for use in engines. Although the present invention and its advantages have been described in detail, it should be understood that several changes, substitutions and alterations can be made thereto without departing from the spirit and scope of the invention as defined by the appended claims. Furthermore, the scope of the present application is not intended to be limited to the particular modalities of the process, machine, manufacture, composition of matter, means, methods and steps described in the description. As one of ordinary skill in the art will readily appreciate from the description of the present invention, "the processes, machines, fabrication, compositions of matter, means, methods or steps, presently existing or later to be developed that carry out substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be used in accordance with the present invention.As a consequence, the appended claims are intended to include within their scope these processes, machines, fabrication, compositions of matter, means, methods or stages.

Claims (85)

1. CLAIMS 1 . A lubricant additive characterized in that it is produced by means of a process comprising: mix an organophosphate and an organofluor compound and reacting the organophosphate and the organofluor compound to produce a reaction mixture comprising the lubricant additive.
2. 2. The lubricant additive produced by the process according to claim 1, characterized in that the organophosphate is ZDDP and the organofluor is PTFE, wherein the PTFE molecules comprise more than 40 carbon atoms.
3. 3. The lubricant additive produced by the process according to claim 1, characterized in that it is produced by a process that further comprises: separating the reaction mixture in phases, at least one phase comprises the additive for lubricants.
4. 4. The lubricant additive produced by the process according to claim 2, characterized in that the ZDDP is selected from the group consisting of: ZDDP neutral (primary), ZDDP neutral (secondary), ZDDP basic, salt ZDDP, ZDDP irradiated, ZDDP not irradiated and combinations thereof.
5. 5. The lubricant according to claim 1, characterized in that the organofluor compound is irradiated PTFE.
6. 6. The lubricant according to claim 2, characterized in that the PTFE comprises compositions of organofluor compounds which include fluoroalkylcarboxylic acids, fluoroarylcarboxylic acids, fluoroalkylarylcarboxylic acids, fluoroalkylsulfonic acids, fluoroarylsulphonic acids or fluoroalkylarylsulfonic acids.
7. 7. The lubricant according to claim 6, characterized in that the compounds have more than one functional group.
8. 8. The lubricant according to claim 7, characterized in that the compounds have any combination of two or more functional groups consisting of carboxylic acids, sulfonic acids, esters, alcohols, amines, amides and mixtures thereof.
9. 9. The lubricant additive produced by the process according to claim 1, characterized in that the mixing further comprises mixing molybdenum disulfide with an organophosphate and an organofluorine composition.
10. 10. The lubricant additive produced by the process according to claim 1, characterized in that the mixing further comprises mixing a metal halide with an organophosphate and an organofluor, and wherein the reaction further comprises reacting the metal halide with the organophosphate and the organofluorine . eleven .
11. The lubricant additive produced by the process according to claim 10, characterized in that the metal halide is selected from the group consisting of: aluminum trifluoride, zirconium tetrafluoride, titanium trifluoride, titanium tetrafluoride, ferric fluoride, chromium difluoride, chromium trifluoride, manganese difluoride, manganese trifluoride, nickel difluoride, stannous difluoride, stannous tetrafluoride and combinations thereof.
12. 12. The lubricant additive produced by the process according to claim 10, characterized in that the mixing further comprises mixing a metal halide, molybdenum disulfide, an organophosphate and an organofluoride, and wherein the reaction further comprises reacting the metal halide, disulfide of molybdenum, organophosphate and organofluoride.
13. 13. The lubricant additive produced by the process according to claim 10, characterized in that the metal halide is from about 0.1 to about 1.0 weight percent ferric fluoride.
14. 14. The lubricant additive produced by the process according to claim 2, characterized in that the ZDDP is ZDDP with a phosphorus content of about 0.01 weight percent to about 0.05 weight percent.
15. 15. The lubricant additive produced by the process according to claim 1, characterized in that the reaction lasts from about 20 minutes to about 24 hours.
16. 16. The lubricant additive produced by the process according to claim 1, characterized in that the reaction comprises reacting at a temperature of about -20 ° C to about 150 ° C.
17. 17. The lubricant additive produced by the process according to claim 1, characterized in that the reaction comprises reacting at a temperature of about 60 ° C to about 150 ° C.
18. 18. A method for making an additive for lubricants, characterized in that it comprises: mix an organophosphate and an organofluor and reacting the organophosphate and organofluor to produce a reaction mixture comprising the additive for lubricants and separating the reaction mixture in solid and liquid phase, at least one phase comprises the additive for lubricants.
19. 19. The method according to claim 18, characterized in that the mixture further comprises mixing molybdenum disulfide with an organophosphate and an organofluor, and wherein the reaction further comprises reacting molybdenum disulfide with an organophosphate and an organofluorine.
20. 20. The method according to claim 1 8, characterized in that the organophosphate is ZDDP and the organofluor is PTFE comprising more than 40 carbon atoms.
21. 21. The lubricant according to claim 16, characterized in that the organofluor compound is irradiated PTF.
22. 22. The method according to claim 1 8, characterized in that the additive for lubricants is in the solid phase.
23. 23. The method according to claim 18, characterized in that the additive for lubricants is in the liquid phase.
24. 24. The lubricant additive according to claim 19, characterized in that the ZDDP is selected from the group consisting of: ZDDP neutral (primary), ZDDP neutral (secondary), ZDDP basic, salt ZDDP, ZDDP irradiated, ZDDP not irradiated and combinations thereof.
25. 25. The lubricant according to claim 20, characterized in that the PTFE comprises compositions of organofluor compounds which include fluoroalkylcarboxylic acids, fluoroarylcarboxylic acids, fluoroalkylarylcarboxylic acids, fluoroalkylsulfonic acids, fluoroarylsulphonic acids or fluoroalkylaryl sulfonic acids.
26. 26. The lubricant according to claim 25, characterized in that the compounds have more than one functional group.
27. 27. The lubricant according to claim 26, characterized in that the compounds have any combination of two or more functional groups consisting of carboxylic acids, sulfonic acids, esters, alcohols, amines, amides and mixtures thereof.
28. 28. The method according to claim 1 8, characterized in that the mixture further comprises mixing a metal halide with an organophosphate and an organofluor, and wherein the reaction further comprises reacting the metal halide with the organophosphate and organofluoride.
29. 29. The method according to claim 28, characterized in that the mixture further comprises mixing molybdenum disulfide with a metal halide, an organophosphate and an organofluor, and wherein the reaction further comprises reacting molybdenum disulfide with a metal halide, an organophosphate and an organofluor.
30. 30. The method according to claim 28, characterized in that the metal halide is selected from the group consisting of: aluminum trifluoride, zirconium tetrafluoride, titanium trifluoride, titanium tetrafluoride, ferric fluoride, chromium difluoride, chromium trifluoride, manganese difluoride, manganese trifluoride, nickel difluoride, stannous difluoride, stannous tetrafluoride and combinations thereof.
31. 3 1. The method according to claim 18, characterized in that the reaction comprises reacting from about 20 minutes to about 24 hours.
32. 32. The method according to claim 1 8, characterized in that the reaction comprises reacting at a temperature from about -20 ° C to about 150 ° C.
33. 33. The method according to claim 18, characterized in that the reaction comprises reacting at a temperature of about 60 ° C to about 150 ° C.
34. 34. The method according to claim 20, characterized in that the ZDDP comprises a phosphorus content of about 0.01 weight percent to about 0.05 weight percent.
35. 35. The method according to claim 28, characterized in that the metal halide is about 0.1 weight percent to about 1.0 weight percent metal halide.
36. 36. A lubricant characterized in that it is produced by a process comprising: form a reaction mixture by reacting an organophosphate and an organofluor and adding at least a portion of the reaction mixture to a lubricant base.
37. 37. A lubricant characterized in that it is produced by the process according to claim 36, wherein the formation of a reaction mixture comprises: forming a reaction mixture by reacting ZDDP and PTFE, wherein the PTFE comprises more than 40 carbon atoms.
38. 38. The lubricant according to claim 36, characterized in that the organofluor compound is irradiated PTFE.
39. 39. The lubricant according to claim 37, characterized in that the PTFE comprises compositions of organofluor compounds including fluoroalkylcarboxylic acids, fluoroarylcarboxylic acids, fluoroalkylarylcarboxylic acids, fluoroalkylsulfonic acids, fluoroarylsulphonic acids or fluoroalkylarylsulfonic acids.
40. 40. The lubricant according to claim 39, characterized in that the compounds have more than one functional group.
41. 41 The lubricant according to claim 40, characterized in that the compounds have any combination of two or more functional groups consisting of carboxylic acids, sulfonic acids, ester, alcohols, amines, amides and mixtures thereof.
42. 42. A lubricant characterized in that it is produced by the process according to claim 36, wherein the formation of a reaction mixture comprises: forming a reaction mixture by reacting molybdenum disulfide with an organophosphate and an organofluoride.
43. 43. The lubricant produced by the process according to claim 36, characterized in that the reaction mixture formed comprises a supernatant, the supernatant is separated from the reaction mixture and added to the base for lubricant.
44. 44. The lubricant produced by the process according to claim 36, characterized in that the reaction mixture formed comprises a precipitate, the precipitate is separated from the reaction mixture and added to the base for lubricant.
45. 45. The lubricant produced by the process according to claim 36, characterized in that the base for lubricant is selected from the group consisting of: GF4 engine oil, GF4 engine oil without ZDDP, fluids for automatic transmission, fluids for crankcase, engine oils, hydraulic oils, gear oils, greases and combinations thereof.
46. 46. The lubricant produced by the process according to claim 36, characterized in that the base for lubricant is a base for lubricant comprising about 0.01 weight percent phosphorus to about 0.1 weight percent phosphorus.
47. 47. The lubricant produced by the process according to claim 36, characterized in that the formation further comprises: forming a reaction mixture by reacting a metal halide with an organophosphate and an organofluorine.
48. 48. The lubricant produced by the process according to claim 47, characterized in that the formation of the reaction mixture comprises: forming a reaction mixture by reacting molybdenum disulfide with a metal halide, an organophosphate and an organofluoride.
49. 49. The lubricant produced by the process according to claim 47, characterized in that the metal halide is selected from the group consisting of: aluminum trifluoride, zirconium tetrafluoride, titanium trifluoride, titanium tetrafluoride, ferric fluoride, chromium difluoride, chromium trifluoride, manganese difluoride, manganese trifluoride, nickel difluoride, stannous difluoride, stannous tetrafluoride and combinations thereof.
50. 50. The lubricant produced by the process according to claim 37, characterized in that the ZDDP is selected from the group consisting of: ZDDP neutral (primary), ZDDP neutral (secondary), ZDDP basic, salt ZDDP, ZDDP irradiated, ZDDP not irradiated and combinations thereof.
51. 51 The lubricant produced by the process according to claim 36, characterized in that the lubricant additive is formed by reacting the organophosphate and the organofluor together for about 20 minutes to about 24 hours.
52. 52. The lubricant produced by the process according to claim 36, characterized in that the lubricant additive is formed by reacting the organophosphate and the organofluor together at a temperature of about -20 ° C to about 150 ° C.
53. 53. The lubricant produced by the process according to claim 36, characterized in that the lubricant additive is formed by reacting the organophosphate and organofluor together at a temperature from about 60 ° C to about 150 ° C.
54. 54. A method for producing a lubricant, characterized in that it comprises: forming a reaction mixture by reacting an organophosphate and an organofluor and adding at least a portion of the reaction mixture to a lubricant base.
55. 55. The method according to claim 54, characterized in that the reaction further comprises: forming a reaction mixture by reacting ZDDP and PTFE, wherein the PTFE comprises more than 40 carbon atoms.
56. 56. The lubricant according to claim 55, characterized in that the PTFE comprises compositions of organofluor compounds which include fluoroalkylcarboxylic acids, fluoroarylcarboxylic acids, fluoroalkylarylcarboxylic acids, fluoroalkylsulfonic acids, fluoroarylsulphonic acids or fluoroalkylarylsulfonic acids.
57. 57. The lubricant according to claim 56, characterized in that the compounds have more than one functional group.
58. 58. The lubricant according to claim 57, characterized in that the compounds have any combination of two or more functional groups consisting of carboxylic acids, sulfonic acids, esters, alcohols, amines, amides and mixtures thereof.
59. 59. The method according to claim 54, characterized in that the reaction mixture comprises a supernatant, the method further comprising: Separate the supernatant from the formed reaction mixture and add at least a portion of the supernatant to the lubricant base.
60. 60. The method according to claim 54, characterized in that the reaction mixture comprises a precipitate, the method further comprising: separating the precipitate from the formed reaction mixture and adding at least a portion of the precipitate to the base for lubricant.
61. 61. The method according to claim 54, characterized in that the formation further comprises forming a reaction mixture by reacting molybdenum disulfide with the organophosphate and organofluoride.
62. 62. The method according to claim 54, characterized in that the formation further comprises forming a reaction mixture by reacting a metal halide with the organophosphate and organofluoride.
63. 63. The method according to claim 62, characterized in that the formation further comprises forming a reaction mixture by reacting molybdenum disulfide with the metal halide, organophosphate and organofluoride.
64. 64. The method according to claim 62, characterized in that the metal halide is selected from the group consisting of: aluminum trifluoride, zirconium tetrafluoride, titanium trifluoride, titanium tetrafluoride, ferric fluoride, chromium difluoride, chromium trifluoride, manganese difluoride, manganese trifluoride, nickel difluoride, stannous difluoride, stannous tetrafluoride and combinations thereof.
65. 65. The method according to claim 55, characterized in that the ZDDP is selected from the group consisting of: ZDDP neutral (primary), ZDDP neutral (secondary), ZDDP basic, salt ZDDP, ZDDP irradiated, ZDDP not irradiated and combinations thereof.
66. 66. The method according to claim 54, characterized in that the base for lubricant is selected from the group consisting of: engine oil GF4, oil for GF4 engines without ZDDP, fluids for automatic transmission, fluids for crankcase, engine oils, hydraulic oils, gear oils, greases and combinations thereof.
67. 67. The method according to claim 54, characterized in that the base for lubricant is a base for lubricant comprising about 0.01 weight percent phosphorus to about 0.1 weight percent phosphorus.
68. 68. The method according to claim 54, characterized in that the reaction mixture is formed by reacting the organophosphate and the organofluor together for about 20 minutes to about 24 hours.
69. 69. The method according to claim 54, characterized in that the reaction mixture is formed by reacting the organophosphate and the organofluor together at a temperature from about -20 ° C to about 150 ° C.
70. 70. The method according to claim 54, characterized in that the reaction mixture is formed by reacting the organophosphate and the organofluor at a temperature from about 60 ° C to about 150 ° C.
71. 71. A lubricant characterized in that it is produced by a process comprising: add an organophosphate and an organofluor to a base for lubricant and react the organophosphate and organofluor in the base for lubricant to form a lubricant.
72. 72. The lubricant produced by the process according to claim 71, characterized in that adding comprises: Add ZDDP and PTFE to a lubricant base, where the PTFE comprises more than 40 carbon atoms.
73. 73. The lubricant according to claim 71, characterized in that the organofluor compound is irradiated PTFE.
74. 74. The lubricant produced by the process according to claim 71, characterized in that the addition further comprises adding molybdenum disulfide, an organophosphate and an organofluor or a base for lubricant and the reaction comprises reacting the molybdenum disulfide, the organophosphate and the organofluorine. in the base for lubricant.
75. 75. The lubricant produced by the process according to claim 71, characterized in that the lubricant formed comprises a supernatant, the supernatant is separated to form the lubricant.
76. 76. The lubricant produced by the process according to claim 71, characterized in that the lubricant formed comprises a solid lubricant.
77. 77. The lubricant produced by the process according to claim 71, characterized in that the base for lubricant is selected from the group consisting of: engine oil GF4, oil for engines GF4 without ZDDP, automatic transmission fluids, fluids for crankcase, motor oils, hydraulic oils, gear oils, greases and combinations thereof.
78. 78. The lubricant produced by the process according to claim 71, characterized in that the base for lubricant is a base for lubricant comprising about 0.01 weight percent phosphorus to about 0.1 weight percent phosphorus.
79. 79. The lubricant produced by the process according to claim 71, characterized in that the addition further comprises adding a metal halide with an organophosphate and organofluor to a base for lubricant and the reaction further comprises reacting a metal halide with organophosphate and organofluor to form a lubricant.
80. 80. The lubricant produced by the process according to claim 79, characterized in that the addition further comprises adding molybdenum disulfide, metal halide, an organophosphate and an organofluor to a base for lubricant and the reaction further comprises reacting molybdenum disulfide, metal halide , an organophosphate and an organofluor to form a lubricant.
81. 81 The lubricant produced by the process according to claim 79, characterized in that the metal halide is selected from the group consisting of: aluminum trifluoride, zirconium tetrafluoride, titanium trifluoride, titanium tetrafluoride, ferric fluoride, chromium difluoride, chromium trifluoride, manganese difluoride, manganese trifluoride, nickel difluoride, stannous difluoride, stannous tetrafluoride, and combinations thereof .
82. 82. The lubricant produced by the process according to claim 72, characterized in that the ZDDP is selected from the group consisting of: ZDDP neutral (primary), ZDDP neutral (secondary), ZDDP basic, salt ZDDP, ZDDP irradiated, ZDDP not irradiated and combinations thereof.
83. 83. The lubricant produced by the process according to claim 71, characterized in that the reaction comprises reacting from about 20 minutes to about 24 hours.
84. 84. The lubricant produced by the process according to claim 71, characterized in that the reaction further comprises reacting at a temperature from about -20 ° C to about 150 ° C.
85. 85. The lubricant produced by the process according to claim 71, characterized in that the reaction further comprises reacting at a temperature of about 60 ° C to about