ES2862123T3 - Low temperature composition - Google Patents

Abstract

Lubricating composition comprising, based on the total weight of the lubricating composition a. at least 55% by weight of a dicarboxylic acid ester component selected from di-isononyladipate (DNA) and di- (2-ethylhexyl) adipate (DOA), b. 10 to 25% by weight of an ethylene-propylene copolymer, and c. 5 to 20% by weight of a monocarboxylic acid ester, in which the ethylene-propylene copolymer (b) has a kinematic viscosity according to JIS K 2283 at 100 ° C in the range of 1000 to 2200 mm2 / s.

Description

DESCRIPTION

Low temperature composition

The present invention relates to the field of lubricants. The lubricant compositions contain a dicarboxylic acid ester and an ethylene-propylene copolymer. The lubricant compositions can be used in a variety of different oil formulations required in motor vehicles.

Technical background

The lubricant compositions available on the market are based on a multitude of different natural or synthetic components. The resulting properties of the various existing lubricant compositions are tailored to specific technical requirements by adding other components and selected combinations thereof. In this way, lubricant compositions are obtained that can meet the complex requirements associated with various special technical applications in the field of motor vehicles, automotive engines and other machines.

Typically, lubricant compositions are needed that provide high shear stability, improved low temperature viscosity, a minimal degree of evaporative loss, good fuel efficiency, acceptable seal compatibility, and excellent wear protection.

An especially desired set of properties in high performance lubrication applications is an excellent low temperature profile indicated by favorable low temperature viscosity in combination with excellent dynamic behavior at high temperatures indicated by high shear stability and high index. viscosity.

Known lubricants that can meet these performance characteristics have been developed in the prior art by adding special thickening agents (viscosity index improving agents). Preferably, the base components of the polyalphaolefin type (PAO) have been modified with thickeners such as polyisobutenes (PIB), oligomeric copolymers (OCP), polymethacrylates (PMA) or high viscosity esters (complex esters) to achieve the desired set of properties.

Document US 5451630 describes the general dilemma when using thickening agents in lubricating compositions, since the increase in viscosity is directly related to the molecular weight of the polymeric thickening agent, while, on the other hand, the shear stability decreases due to to the greater tendency to breakage under shear and high temperature conditions.

US 5451630 further suggests oligomeric copolymers which have been shown to provide good shear stability to lubricating compositions.

In WO 2007/144079 A2, a greater number of lubricant compositions have been described which include a variety of different thickening agents such as PIB, OCP, PMA and high viscosity esters which have proven to be generally applicable as viscosity index improvers.

Document US2010 / 093579 discloses a motor lubricant comprising at least 15% by weight of at least one diester and not more than 20% by weight of additives, wherein said at least one diester, or the mixture of said diesters if more than one is present, has a kinematic viscosity of not more than 3.3, a viscosity index of at least 130, a pour point of not more than -30 ° C, and a Noack evaporation loss of not more than 15 % in weigh.

US 3634 249 discloses a lubricating composition comprising a major amount of a base oil that does not meet the viscosity requirements of a multigrade oil, selected from the group consisting of a mineral oil and a synthetic ester lubricating oil, and an amount viscosity enhancement of at least 1% by weight and sufficient to impart the viscosity requirements of a multigrade oil to the base oil of an oil copolymer liquid fraction.

Furthermore, dicarboxylic acid esters such as DIDA (diisodecyl adipate), DITA (diisotradecyl adipate) or TMTC (trimethylolpropane caprylate) have also been added to such lubricating compositions as solubilizers for polar additive types.

However, there is a continuing need for new lubricant compositions that exceed the performance characteristics of existing lubricant compositions. This is particularly important for lubricating compositions that are designed for use in extreme conditions. It is especially difficult to develop lubricating compositions that offer the desired excellent rheological properties both at very low temperatures and at elevated temperatures. Surprisingly, the present invention provides lubricant compositions comprising the combination of a dicarboxylic acid ester component with an ethylene-propylene copolymer having excellent high temperature dynamic behavior and an unusually high viscosity index, while the viscosity corresponding to very low temperatures is still only moderate. Another important property is the high permanent shear stability of the lubricant compositions according to the present invention.

Description of the invention

The present invention relates to a lubricating composition comprising, based on the total weight of the lubricating composition

a) at least 55% by weight of a dicarboxylic acid ester component selected from diisononyladipate (DNA) and di- (2-ethylhexyl) adipate (DOA),

b) 10 to 25% by weight of an ethylene-propylene copolymer, and

c) 5 to 20% by weight of a monocarboxylic acid ester,

wherein the ethylene-propylene copolymer (b) has a kinematic viscosity according to JIS K 2283 at 100 ° C in the range of 1000 to 2200 mm2 / s.

In another preferred embodiment, the lubricant compositions defined above also have a kinematic viscosity according to the industrial standard DN 51562-1 of not more than 1600 mm2 / s at -30 ° C and of at least 7.5 mm2 / s at 100 ° C.

In another preferred embodiment, the lubricant composition has a viscosity index according to DIN ISO 2909 of at least 160, preferably of at least 180.

In another preferred embodiment, the lubricant composition further comprises a base oil component having a kinematic viscosity according to DIN 51562-1 of approximately 1 to 5 mm2 / s at 100 ° C, preferably a PAO-2 component.

In another preferred embodiment, the monocarboxylic acid ester is selected from the list consisting of 2-ethylhexylcocoate, 2-ethylhexylcocoate, 2-ethylhexylpalmitate, 2-ethylhexyl stearate, and 2-ethylhexyltallowate, and mixtures thereof.

In another preferred embodiment, the ratio of the dicarboxylic acid ester component to the oligomeric copolymers in the lubricant compositions according to the present invention is in the range of 2: 1 to 19: 1, preferably 3: 1 to 10: 1 in based on the relative weight of these components in the lubricant compositions according to the present invention.

In another preferred embodiment, the lubricating composition further comprises an additive component that is present in an amount of 0.1 to 20% by weight of the total lubricating composition.

In another preferred embodiment, the lubricating compositions are used as vehicle transmission oil, axle oil, industrial transmission oil, compressor oil, turbine oil, hydraulic oil or motor oil.

It is further preferred that the kinematic viscosity of the aforementioned lubricant compositions, based on the industrial standard DIN 51562-1, at a temperature of -30 ° C, is not more than 1600 mm2 / s, preferably not more than 1550 mm2 / s, and even not higher than 1500 mm2 / s, and / or, preferably, that the kinematic viscosity based on the industrial standard DIN 51562-1, at a temperature of 100 ° C, is at least 7.0 mm2 / s, preferably at least 7.5 mm2 / s, and even more preferably at least 8.0 mm2 / s.

The kinematic viscosity of the lubricant compositions according to the present invention based on the industrial standard DIN 51562-1 at a temperature of -30 ° C is at least 500 mm2 / s, more preferably at least 700 mm2 / s, and even more preferably at least 900 mm2 / s.

The kinematic viscosity based on the industry standard DIN 51562-1 at a temperature of 40 ° C is at least 25 mm2 / s, preferably at least 30 mm2 / s, and even more preferably at least 35 mm2 / s.

The kinematic viscosity based on the industry standard DIN 51562-1 at a temperature of 100 ° C is at least 7.0 mm2 / s, preferably at least 7.5 mm2 / s, and even more preferably at least 8.0 mm2 / s.

The rheological profile of the lubricating compositions according to the present invention is defined especially by a kinematic viscosity based on the industrial standard DIN 51562-1 at a temperature of -30 ° C which is not higher than 1600 mm2 / s, preferably not higher than 1550 mm2 / s, and even more preferably not more than 1500 mm2 / s and a kinematic viscosity based on the industrial standard DIN 51562-1 at a temperature of 100 ° C which is at least 7.0 mm2 / s, preferably at least 7, 5mm2 / s, and even more preferably at least 8.0mm2 / s.

Furthermore, the rheological profile of the lubricant compositions according to the present invention is characterized by a viscosity index based on the DIN ISO 2909 industrial standard of at least 160, more preferably of at least 190, and even more preferably of at least 200.

The lubricant compositions according to the present invention have a pour point according to DIN ISO 3016 not higher than -50 ° C, preferably not higher than -60 ° C, and even more preferably not higher than -70 ° C.

Preferably, the lubricant compositions according to the present invention have a kinematic viscosity based on the industrial standard DIN 51562-1 at a temperature of -30 ° C which is not higher than 1600 mm2 / s, preferably not higher than 1550 mm2 / s, and even not higher than 1500 mm2 / s, and a kinematic viscosity based on the industrial standard DIN 51562-1 at a temperature of 100 ° C which is at least 7.0 mm2 / s, preferably at least 7.5 mm2 / s , and even more preferably at least 8.0 mm2 / s, and a viscosity index based on the DIN ISO 2909 industry standard of at least 160, more preferably at least 180, and even more preferably at least 200.

The lubricant compositions according to the present invention include the following components which are described in more detail below.

The lubricant compositions according to the present invention include as a first essential component a dicarboxylic acid ester component.

The amount of the dicarboxylic acid ester component in the lubricating compositions according to the present invention is in the range of 55 to 85% by weight, and even more preferably in the range of 65 to 80% by weight based on the total weight of the lubricating composition.

In a particularly preferred embodiment, the dicarboxylic ester component according to the present invention is diisononyl adipate (DNA).

Diisononyl adipate (DNA) is obtained by reacting a mixture comprising adipic acid and a mixture of alcohols comprising 1-nonanol, monomethyloctanols, dimethylheptanols and monoethylheptanols, so that the polyester has a viscosity at 40 ° C of the order of 5 at 15 mm2 / s determined according to DIN 51562-1. The viscosity of the polyester at 40 ° C is preferably 6 to 14 mm2 / s, more preferably 7 to 13 mm2 / s, and more preferably 8 to 12 mm2 / s determined according to DIN 51562-1.

Polyesters prepared by reacting a mixture comprising adipic acid and a mixture of alcohols comprising 1-nonanol, monomethyloctanols, dimethylheptanols and monoethylheptanols preferably have a density at 20 ° C according to DIN 51757 of 0.85 to 1.00 g / cm3, more preferably 0.88 to 0.95 g / cm3 and more preferably 0.90 to 0.94 g / cm3. Refractive index No. 20 according to DIN 51423 is preferably 1,400 to 1,500, more preferably 1,420 to 1,480, and more preferably 1,440 to 1,460.

The mixture of alcohols comprising 1-nonanol, monomethyloctanols, dimethylheptanols and monoethylheptanols is obtained particularly advantageously in a process comprising two or more stages and starting from a hydrocarbon mixture comprising butenes. In a first stage, the butenes dimerize to give a mixture of isomeric octenes. The octene mixture is then hydroformylated to give Cg aldehydes and then hydrogenated to give the alcohol mixture. In this reaction sequence, specific and defined parameters must be respected, at least during the dimerization of the butenes, and preferably during the dimerization of the butenes and the hydroformylation.

It is therefore preferable that the isomeric octene mixture is obtained by contacting a hydrocarbon mixture comprising butenes with a heterogeneous catalyst comprising nickel oxide. The isobutene content of the hydrocarbon mixture is preferably 5% by weight or less, in particular 3% by weight or less, particularly preferably 2% by weight or less, and more preferably 1.5% by weight or less, based in each case on the total content of butene. A suitable hydrocarbon stream is known as the C4 cut, a mixture of butenes and butanes, available in large quantities from FCC plants or steam crackers. A starting material used with particular preference is that known as raffinate II, which is a C4 cut depleted in isobutene.

A preferred starting material comprises from 50 to 100% by weight, preferably from 80 to 95% by weight, of butenes and from 0 to 50% by weight, preferably from 5 to 20% by weight, of butanes. The following composition of the butenes can be given as a general guide of quantities:

1-butene from 1 to 98% by weight,

cis-2-butene from 1 to 50% by weight,

trans-2-butene from 1 to 98% by weight, and

isobutene up to 5% by weight.

Possible catalysts are catalysts known per se and comprising nickel oxide, as described, for example, by O'Connor et al. in Catalysis Today, 6, (1990) p. 329. Supported nickel oxide catalysts can be used, and possible support materials are silica, alumina, aluminosilicates, layered aluminosilicates, and zeolites. Particularly suitable catalysts are the precipitation catalysts obtained by mixing aqueous solutions of nickel salts and silicates, for example sodium silicate and sodium nitrate, and, where appropriate, other components, such as aluminum salts, for example example aluminum nitrate, and calcining.

Particular preference is given to catalysts consisting essentially of NiO, SiO2, TiO2 and / or ZrO2, and also, where appropriate, AhO3. A more preferred catalyst comprises, as significant active constituents, 10 to 70% by weight of nickel oxide, 5 to 30% by weight of titanium dioxide and / or zirconium dioxide and 0 to 20% by weight of oxide. aluminum, the remainder being silicon dioxide. Such a catalyst is obtained by precipitating the catalyst composition at a pH of 5 to 9 by adding an aqueous solution comprising nickel nitrate to an aqueous solution of alkali metal water glass comprising titanium dioxide and / or zirconium dioxide, filtering , drying and annealing at a temperature of 350 to 650 ° C. For the details of the preparation of these catalysts, reference can be made to DE-A 4339713. The entire content of the disclosure of said publication is incorporated herein by reference. .

The hydrocarbon mixture comprising the butenes is brought into contact with the catalyst, preferably at temperatures from 30 to 280 ° C., in particular from 30 to 140 ° C. and particularly preferably from 40 to 130 ° C. This preferably takes place at a pressure of 1 to 30 MPa, in particular 1.5 to 10 MPa and particularly preferably 2 to 8 MPa. In this case, the pressure is set so that the olefin-rich hydrocarbon mixture is liquid or is in a supercritical state at the selected temperature.

Examples of suitable reactors for contacting the hydrocarbon mixture with the heterogeneous catalyst are tube bundle reactors and shaft furnaces. Shaft furnaces are preferred because the investment costs are lower. The dimerization can be carried out in a single reactor, in which the oligomerization catalyst can have been arranged in one or more fixed beds. Another way is to use a reactor cascade composed of two or more, preferably two, reactors arranged in series, where the dimerization of the butene in the reaction mixture is led to only partial conversion as it passes through the reactor or reactors preceding the latter. cascade reactor, and the desired final conversion is not achieved until the reaction mixture passes through the last reactor in the cascade. The dimerization of butene preferably takes place in an adiabatic reactor or in a cascade of adiabatic reactors.

After leaving the reactor or, respectively, the last reactor of a cascade, the octenes formed and, where appropriate, the higher oligomers, are separated from the butenes and unconverted butanes in the discharge of the reactor. The oligomers formed can be purified in a subsequent vacuum fractionation step, yielding a pure octene fraction. During the dimerization of butene, small amounts of dodecenes are generally also obtained. These are preferably separated from the octenes before the subsequent reaction.

In a preferred embodiment, part or all of the reactor discharge is returned, freed from the oligomers formed and consisting essentially of unconverted butenes and butanes. It is preferable to select the return ratio so that the concentration of oligomers in the reaction mixture does not exceed 35% by weight, preferably 20% by weight, based on the hydrocarbon mixture of the reaction. This measure increases the selectivity of the dimerization of butene with respect to those octenes which, after hydroformylation, hydrogenation and esterification, give a particularly preferred alcohol mixture.

The octenes obtained are converted, in the second stage of the process, by hydroformylation using synthesis gas in a manner known per se, into aldehydes having an additional carbon atom. Hydroformylation of olefins to prepare aldehydes is known per se and is described, for example, in J. Falbe, (ed.): New Synthesis with Carbon monoxide, Springer, Berlin, 1980. Hydroformylation takes place in the presence of homogeneously dissolved catalysts in the reaction medium. The catalysts generally used here are compounds or complexes of metals of transition group VIII, specifically compounds of Co, Rh, Ir, Pd, Pt or Ru, or complexes of these metals, either unmodified or modified, for example, using compounds containing amine or phosphine.

The hydroformylation preferably takes place in the presence of a cobalt catalyst, in particular dicobaltctacarbonyl [CO2 (CO) s]. It is preferably carried out at a temperature of 120 to 240 ° C, in particular 160 to 200 ° C, and under a synthesis gas pressure of 15 to 40 MPa, in particular 25 to 35 MPa. The hydroformylation preferably takes place in the presence of water. The ratio of hydrogen to carbon monoxide in the synthesis gas mixture used is preferably in the range of 70:30 to 50:50, in particular 65:35 to 55:45.

The cobalt catalyzed hydroformylation process can be carried out as a multi-stage process comprising the following 4 stages: catalyst preparation (precarbonylation), catalyst extraction, olefin hydroformylation and removal of the catalyst from the reaction product (decobaltization) . In the first stage of the process, precarbonylation, an aqueous solution of cobalt salt, for example cobalt formate or Cobalt acetate, as a starting material, is reacted with carbon monoxide and hydrogen to prepare the catalyst complex necessary for hydroformylation. In the second stage of the process, the extraction of the catalyst, the cobalt catalyst prepared in the first stage of the process is extracted from the aqueous phase using an organic phase, preferably using the olefin to be hydroformylated. In addition to olefin, it is occasionally advantageous to use reaction products and hydroformylation by-products for catalyst extraction, provided that these are insoluble in water and liquids under the selected reaction conditions. After phase separation, the organic phase loaded with the cobalt catalyst is introduced into the third stage of the process, hydroformylation. In the fourth stage of the process, the decobalization, the organic phase of the reactor discharge is freed from the cobalt carbonyl complexes in the presence of the process water, which may comprise formic acid or acetic acid, by treatment with oxygen or air. During this process, the cobalt catalyst is destroyed by oxidation and the resulting cobalt salts are extracted back into the aqueous phase. The aqueous solution of cobalt salts obtained from the decobaltization is returned to the first stage of the process, precarbonylation. The crude hydroformylation product obtained can be fed directly to the hydrogenation. Another way is to isolate a Cg fraction in the usual way, for example by distillation, and feed this to hydrogenation.

The formation of the cobalt catalyst, the extraction of the cobalt catalyst in the organic phase and the hydroformylation of the olefins can also be carried out in a single stage process in the hydroformylation reactor.

Examples of cobalt compounds that can be used are cobalt (II) chloride, cobalt (II) nitrate, amine complexes or hydrate complexes thereof, cobalt carboxylates, such as cobalt formate, acetate cobalt, cobalt ethylhexanoate and cobalt naphthenate (Co salts of naphthenic acid), and also the cobalt caprolactamate complex. Under the conditions of hydroformylation, catalytically active cobalt compounds are formed in situ as cobalt carbonyls. It is also possible to use cobalt carbonyl complexes such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl, and hexadecacarbonyl hexacobalt.

The aldehyde mixture obtained during hydroformylation is reduced to give primary alcohols. Immediate partial reduction generally occurs under the hydroformylation conditions, and it is also possible to control the hydroformylation such that essentially complete reduction occurs. However, the hydroformylation product obtained is usually hydrogenated in a later stage of the process using hydrogen gas or a hydrogen-containing gas mixture. Hydrogenation usually takes place in the presence of a heterogeneous hydrogenation catalyst. The hydrogenation catalyst used can comprise any desired catalyst suitable for hydrogenating aldehydes to primary alcohols. Examples of suitable commercially available catalysts are copper chromite, cobalt, cobalt compounds, nickel, nickel compounds, including small amounts of chromium or other promoters, and mixtures of copper. , nickel and / or chromium. Nickel compounds are generally in a form supported on support materials, such as alumina or diatomaceous earth. It is also possible to use catalysts comprising noble metals, such as platinum or palladium.

A suitable process for carrying out the hydrogenation is a drip flow process, in which the mixture to be hydrogenated and the hydrogen gas or, respectively, the hydrogen-containing gas mixture are passed, for example simultaneously, by a fixed bed of hydrogenation catalyst.

The hydrogenation preferably takes place at a temperature of 50 to 250 ° C, in particular 100 to 150 ° C, and at a hydrogen pressure of 5 to 35 MPa, in particular 15 to 30 MPa. The desired isononanol fraction in the reaction discharge obtained during hydrogenation can be separated by fractional distillation of the C8 hydrocarbons and the higher boiling products.

Gas chromatographic analysis of the resulting alcohol mixture can give the relative amounts of the individual compounds (the percentages listed are percentages per gas chromatogram area):

The proportion of 1-nonanol in the alcohol mixture is preferably 6 to 16% by weight, more preferably 8 to 14% by weight, relative to the total weight of the alcohol mixture.

The proportion of the monomethyloctanols is preferably 25 to 55% by weight, more preferably 35 to 55% by weight, and it is particularly preferable that 6-methyl-1-octanol and 4-methyl-1-octanol together constitute the less than 25% by weight, very particularly preferably at least 35% by weight, relative to the total weight of the alcohol mixture.

The proportion of dimethylheptanols and monoethylheptanols is preferably 15 to 60% by weight, more preferably 20 to 55% by weight, and it is preferable that 2,5-dimethyl-1-heptanol, 3-ethyl-1 Heptanol and 4,5-dimethyl-1-heptanol together constitute at least 15% and in particular 20% by weight, relative to the total weight of the alcohol mixture. The proportion of the hexanols is preferably 4 to 10% by weight and more preferably 5 to 10% by weight, relative to the total weight of the alcohol mixture.

The alcohol mixture preferably consists of 70 to 100%, more preferably 70 to 99%, more preferably 80 to 98%, and even more preferably 85 to 95%, of a mixture of 1-nonanol, monomethyloctanols, dimethylheptanols and monoethylheptanols, relative to the total weight of the alcohol mixture.

Preferably, the alcohol mixture contains a proportion of 6% by weight to 16% by weight of 1-nonanol, 25% by weight to 55% by weight of monomethyloctanols, 10% by weight to 30% by weight of dimethylheptanols and 7% by weight to 15% by weight of monoethylheptanols, relative to the total weight of the alcohol mixture.

Preferably, the alcohol mixture is present in a molar ratio in the range of 1: 1 to 2: 1, more preferably in a molar ratio in the range of 1: 1 to 1.3: 1, relative to adipic acid. .

The density of the alcohol mixture of the invention at 20 ° C is preferably 0.75 to 0.9 g / cm3, more preferably 0.8 to 0.88 g / cm3, and more preferably 0.82 to 0.84 g / cm3, according to DIN 51757. The refractive index # 20 is preferably 1.425 to 1.445, more preferably 1.43 to 1.44 and more preferably 1.432 to 1.438. The boiling range at atmospheric pressure is preferably 190 to 220 ° C, more preferably 195 to 215 ° C, and more preferably 200 to 210 ° C.

In a particularly preferred embodiment, the dicarboxylic ester component according to the present invention is a di- (2-ethylhexyl) -adipate (DEHA or ^{D or A).}

Di- (2-ethylhexyl) -adipate preferably has a dynamic viscosity at 20 ° C in the range of 12 to 16 mPa.s according to DIN 51562, calculated from the measured kinematic viscosity and the multiplication of the kinematic viscosity measured by density. Di- (2-ethylhexyl) -adipate has a density at 20 ° C in the range of 0.920 to 0.930 g / cm3 determined according to DIN 51757 and a pour point <-50 ° C determined according to DIN ISO 3016 as a lubricant.

The dynamic viscosity of di- (2-ethylhexyl) -adipate at 20 ° C is preferably 13 to 15 mm2 / s determined according to DIN 51562.

Preferably, the di- (2-ethylhexyl) -adipate has a density in the range of 0.922 to 0.928 g / cm3, more preferably in the range of 0.924 to 0.926 g / cm3. Density is determined according to DIN 51757. A preferred example for the di- (2-ethylhexyl) -adipate component is Plastomoll® DOA, which is commercially available from BASF SE.

In another particularly preferred embodiment of the present invention, the lubricant composition according to the present invention includes at least one of the above particularly preferred dicarboxylic acid esters, while further comprising an additional monocarboxylic acid ester component.

The additional monocarboxylic acid ester component is preferably obtained by reacting one or more monoalcohols with a monocarboxylic acid.

Monocarboxylic acids preferably contain at least 4 carbons, preferably C6 to C30, more preferably Ce to C20, acids such as straight chain saturated fatty acids, including caprylic acid, capric acid, myristic acid, palmitic acid, stearic acid, araic acid and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids, such as oleic acid, or their mixtures.

The monoalcohol is preferably 2-ethylhexanol, propylheptanol or the like.

Other typical components of monocarboxylic acid esters are represented by 2-ethylhexyl oleate, for example, commercially available as Synative ES EHO® (BASF SE), 2-ethylhexyl cocoate, for example, commercially available as Synative ES EHK® (BASF SE), 2-ethylhexyl palmitate, for example, commercially available as Synative ES EHPA® (BASF SE), 2-ethylhexyl stearate, for example, commercially available as Synative ES EHS® (BASF SE). . ex. commercially available as Synative ES EHPA® (BASF SE), 2-ethyl stearate, e.g. ex. commercially available as Synative ES EHS® (BASF SE), 2-ethyl tallowate, e.g. ex. commercially available as Synative ES EHTI® (BASF SE).

The amount of additional monocarboxylic acid ester in the lubricating compositions according to the present invention in the range of 5 to 20% by weight, or even more preferably in the range of 10 to 18% by weight based on the total weight of the lubricating composition .

In another particularly preferred embodiment of the present invention, the lubricant composition according to the present invention includes at least one of the above particularly preferred dicarboxylic acid esters, an additional monocarboxylic acid ester, further comprising a further complex carboxylic acid ester component.

A complex carboxylic acid ester according to the present invention is defined as an ester that is formed from polyols with dicarboxylic acids and / or monocarboxylic acids.

The complex monocarboxylic acid ester component is preferably obtained by reacting one or more polyhydric alcohols, preferably hindered polyols such as neopentyl polyols, for example neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol, trimethylol propane, trimethylol butane, pentaerythritol and dipentaerythritol with monocarboxylic acids containing at least 4 carbons, typically the C5 to C30 acids as straight chain saturated fatty acids, including caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, araic acid and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids, such as oleic acid, or their mixtures, with polycarboxylic acids.

For example, a neopentyl glycol ester of at least one monocarboxylic acid having 7 to 10 carbon atoms and of at least one other ester of a different hindered polyol with a monocarboxylic acid having 5 to 10 carbon atoms is preferred. Other preferred polyols are trimethylolpropane, pentaerythritol or dipentaerythritol. Another typical complex carboxylic acid ester that is preferably used in lubricating compositions according to the present invention is a complex carboxylic acid ester commercially available as Synative ES 3345® (BASF SE).

The amount of additional complex carboxylic acid ester in the lubricating compositions according to the present invention is in the range of 0 to 20% by weight, preferably in the range of 2 to 15% by weight, or even more preferably in the range of 5 to 10% by weight based on the total weight of the lubricant composition.

In another particularly preferred embodiment of the present invention, the lubricant composition according to the present invention comprises at least one of the four particularly preferred dicarboxylic acid esters above, optionally an additional monocarboxylic acid ester and / or a complex carboxylic acid ester component additional, further comprising an additional Guerbet alcohol component.

The Guerbet term alcohols is used for the 2-alkyl substituted 1-alkanols whose industrial synthesis is described, inter alia, in H. Machemer, Angewandte Chemie, Vol. 64, pages 213-220 (1952) and in G. Dieckelmann and HJ Heinz in "The Basics of Industrial Oleochemistry", pages 145-145 (1988). In a preferred embodiment, the Guerbet alcohol is derived, at least in part, from 2-hexyl decanol, 2-hexyl dodecanol, 2-octyl decanol and / or 2-octyl dodecanol.

Particularly preferred Guerbet alcohols are 2-hexyldecyl alcohol, for example, commercially available as Synative AL G 16® (BASF SE), or 2-octyldodecyl alcohol, for example, commercially available as Synative AL G 20® (B ^a S ^f SE).

The amount of additional Guerbet alcohol component in the lubricant compositions according to the present invention is in the range of 0 to 20% by weight, preferably in the range of 2 to 15% by weight, or even more preferably in the range of 5 to 10% by weight based on the total weight of the lubricant composition.

The base oil (or base material) to be used in the lubricating compositions according to the present invention is an optional component.

The base oil to be used in the lubricating compositions according to the present invention is an inert oil component of the solvent type in the lubricating compositions according to the present invention.

Preferably, the lubricating compositions according to the present invention further comprise base oils selected from the group consisting of mineral oils (Group I, II or III oils), polyalphaolefins (Group IV oils), polymerized and interpolymerized olefins, alkylnaphthalenes, oxide polymers alkylene, silicone oils and phosphate esters (Group V oils).

Definitions for base oils according to the present invention are the same as found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Department of Industrial Services, Fourteenth Edition, December 1996, Addendum 1 , December 1998. Said publication classifies the base matters as follows:

a) Group I base oils contain a percentage of saturates less than 90 percent and / or a percentage of sulfur greater than 0.03 percent and have a viscosity index greater than or equal to 80 and less than 120 using the procedures specified in the following table.

b) Group II base oils contain a percentage of saturates greater than or equal to 90 percent and a percentage of sulfur less than or equal to 0.03 percent and have a viscosity index greater than or equal to 80 and less than 120 using the test procedures specified in the following table.

c) Group III base oils contain a percentage of saturates equal to or greater than 90 percent and a percentage of sulfur equal to or less than 0.03 percent, and have a viscosity index equal to or greater than 120, using the test procedures listed in the table below

Base Matter Analytical Procedures:

Test Procedure Property

Saturated ASTM D 2007

Viscosity index ASTM D 2270

Sulfur ASTM D 2622

ASTM D 4294

ASTM D 4927

ASTM D 3120

d) Group IV base oils contain polyalphaolefins. Lower viscosity synthetic fluids suitable for the present invention include polyalphaolefins (PAOs) and synthetic oils derived from hydrocracking or hydroisomerization of high-boiling Fischer Tropsch fractions, including waxes. Both are saturated base oils with low levels of impurities, consistent with their synthetic origin. Hydro-isomerized Fischer Tropsch waxes are very suitable base oils, which comprise saturated components of iso-paraffinic character (resulting from the isomerization of the predominant nparaffins of Fischer Tropsch waxes) that give a good mixture of high viscosity index and low pour point. Processes for the hydro-isomerization of Fischer Tropsch waxes are described in US Patents 5,362,378; 5,565,086; 5,246,566 and 5,135,638, as well as in EP 710710, EP 321302 and EP 321304.

Suitable polyalphaolefins for lubricant compositions according to the present invention include known PAO materials that typically comprise relatively low molecular weight hydrogenated polymers or oligomers of alphaolefins including but not limited to alphaolefins from C2 to about C32, with Ce alphaolefins being preferred. at about C16, such as 1-octene, 1-dodecene, and the like. Preferred polyalphaolefins are poly-1-octene, poly-1-decene, and poly-1-dodecene, although higher olefin dimers in the C14 to C18 range provide low viscosity base stock stocks.

Terms like PAO-2, PAO 4, PAO 6 or PAO 8 represent preferred polyalphaolefins while these terms are commonly used specifications for different classes of polyalphaolefins characterized by their respective viscosity. For example, PAO 2 refers to a particularly preferred class of polyalphaolefins according to the present invention, which typically have a viscosity in the range of 2 mm2 / s at 100 ° C. There are a variety of commercially available compositions for these specifications.

Low viscosity PAO fluids suitable for lubricant compositions according to the present invention may conveniently be made by polymerization of an alphaolefin in the presence of a polymerization catalyst such as Friedel-Crafts catalysts including, for example, aluminum trichloride, aluminum trifluoride boron or boron trifluoride complexes with water, alcohols such as ethanol, propanol, or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate. For example, the procedures disclosed by US Patents 4,149,178 or 3,382,291 may be conveniently used herein. Other descriptions of the synthesis of PAO are found in the following US patents: 3,742,082 (Brennan); 3,769,363 (Brennan); 3,876,720 (Heilman); 4,239,930 (Allphin); 4,367,352 (Watts); 4,413,156 (Watts); 4,434,408 (Larkin); 4,910,355 (Shubkin); 4,956,122 (Watts); and 5,068,487 (Theriot).

e) Group V base oils contain any base material not described in Groups I to IV. Examples of Group V base oils are alkylnaphthalenes, alkylene oxide polymers, silicone oils, and phosphate esters.

The carboxylic acid esters that are widely considered in the literature as belonging to group V base oils are not understood according to the present invention as base oils (base materials) or even group V base oils, but are classified or separately defined as the dicarboxylic acid ester or monocarboxylic acid ester component that is essential or at least optional for the present invention, respectively.

Synthetic base oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly (1-hexenes), poly (1-octenes), poly (1-decene)); alkylbenzenes (eg, dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl) benzenes); polyphenyls (for example, biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologues.

Alkylene oxide polymers and interpolymers and their derivatives in which the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic base oils. They are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and alkyl and aryl ethers of polyoxyalkylene polymers (for example, methylpolypropylene glycol ether having a molecular weight of 1000 or ether polyethylene glycol diphenyl having a molecular weight of 1000 to 1500); and the mono and polycarboxylic esters thereof, for example acetic acid esters, C3-C8 fatty acid mixed esters and C13 Oxo acid diester of tetraethylene glycol.

Silicone-based oils, such as polyalkyl, polyaryl, polyalkoxysilicone, or polyaryloxysilicone oils, and silicate oils comprise another useful class of synthetic base oils; Such base oils include tetraethyl silicate, tetraisopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methyl-2-ethylhexyl) silicate, tetra- (p-tert- butyl-phenyl), hexa- (4-methyl-2-ethylhexyl) disiloxane, oli (methyl) siloxanes and poly (methylphenyl) siloxanes. Other synthetic base oils are liquid phosphorus-containing acid esters (eg, tricresyl phosphate, trioctyl phosphate, dietary decylphosphonic acid ester) and polymeric tetrahydrofurans.

The base oil can also include so-called gas-to-liquid (GTL) base materials. Suitable GTL base materials which can be used in the present invention are described, for example, in WO 2010/021751 A1 and which are incorporated herein by reference.

The base oil component has a kinematic viscosity according to DIN 51562-1 at 100 ° C in the range of 1 to 8 mm2 / s, preferably 1 to 5 mm2 / s, or even more preferably 1 to 3 mm2 / s. PAO-2 is the most preferred base oil to be used in the lubricating compositions according to the present invention.

The relative amount of base oil in the lubricating compositions according to the present invention is in the range of 0 to 50% by weight, preferably in the range of 5 to 35, or even more preferably in the range of 10 to 25% by weight in based on the total amount of the lubricating composition.

The oligomeric copolymers are preferably ethylene-propylene copolymers having a number average molecular weight Mn according to DIN 55672 within the range of about 20,000 to about 150,000 kg / mole, preferably about 40,000 to about 120,000 kg / mole, or even more preferably 60,000 to 100,000 kg / mol. Such oligomeric copolymers are described, for example, in US 5451630. Oligomeric copolymers are typically used in the art as viscosity modifying agents in lubricant compositions with improved shear stability. The ethylene propylene copolymers according to the present invention have a kinematic viscosity according to JIS K 2283 at 100 ° C in the range from 500 to 3000 mm2 / s, preferably from 900 to 2500 mm2 / s, or even more preferably from 1000 to 2200 mm2 / s.

The ethylene propylene copolymers according to the present invention have a kinematic viscosity according to JIS K 2283 at 40 ° C in the range of 10,000 to 50,000 mm2 / s, preferably 15,000 to 40,000 mm2 / s, or even more preferably 18,000 to 38,000 mm2 / s.

The ethylene propylene copolymers according to the present invention have a pour point according to JIS K 2269 in the range of -20 ° C to -5 ° C, preferably -15 ° C to -10 ° C, or even more preferably - 12.5 to -10 ° C. Another preferred type of ethylene propylene copolymers is commercially available as LU-CANT ™ (Mitsui Chemicals), preferably LUCANT ™ 2000 and LUCANT ™ 1100.

The amount of oligomeric copolymer, preferably ethylene propylene copolymer, is in the range of about 5 to 30% by weight, preferably 10 to 25% by weight, or even more preferably 12 to 20% by weight based on the total weight of the lubricating composition.

The ratio of the dicarboxylic acid ester component to the oligomeric copolymers in the lubricant compositions according to the present invention is in the range of 2: 1 to 19: 1, preferably 3: 1 to 10: 1, even more preferably in the range from 4: 1 to 6: 1 based on the relative weight of these components in the lubricant compositions according to the present invention.

The lubricating composition according to the present invention comprising oligomeric copolymers as viscosity index improvers may further comprise additional viscosity index improvers. Viscosity index improvers are thickening components that are capable of increasing the viscosity of a lubricating composition when added to it.

Other suitable agents for improving the viscosity index are conventional polyisobutenes (PIB) without terminal double bonds, highly reactive polyisobutenes with terminal double bonds, polymethacrylates (PMA) or the like.

However, in a preferred embodiment of the present invention, the aforementioned additional viscosity index improvers, apart from oligomeric copolymers, are absent from the lubricant compositions according to the present invention, either individually or in combination.

Accordingly, in a preferred embodiment of the present invention, conventional polyisobutenes (PIB) without terminal double bonds and / or highly reactive polyisobutenes are absent from lubricant compositions according to the present invention.

The term "conventional polyisobutenes", as used in the present application, refers to polyisobutenes that do not have terminal double bonds. Conventional polyisobutenes therefore differ in this latter respect from highly reactive polyisobutenes which have a high degree of terminal double bonds. A preferred conventional polyisobutene is Lubrizol 8406®.

Highly reactive polyisobutene polymers are understood in their most generic form in the context of the present invention as a polyisobutene polymer having at least 60 mole% terminal double bonds based on the total number of double bonds in the polymer. The amount of terminal double bonds in highly reactive polyisobutenes can be determined following the procedure mentioned in US 5962604 using 13C-NMR spectroscopy based on the relative peak areas corresponding to the C-alpha and C-beta carbon atom signals. (114.4 ppm and 143.6 ppm chemical shift), respectively.

In another preferred embodiment of the present invention, poly (meth) acrylates (PMA) are absent from the lubricant compositions according to the present invention.

Poly (meth) acrylates (PMA) are (meth) acrylic acid esters that can provide increased shear stability in lubricating compositions. Such poly (meth) acrylates are described, for example, in DE 3544061. Typical PMAs used in the art are those of the commercial Viscoplex® series of additives. Preferred PMAs are alkylmethacrylate (Viscoplex 0-101), alkylmaleate-alpha-olefin copolymer I (Gear-Lube 7930), alkyl fumarate-alpha-olefin copolymer I (Gear-Lube 7960), and the like.

The lubricant compositions according to the present invention may also comprise an additive component. The additive component used in the present invention may include a package of additives and / or performance additives.

The additive package as used in the present invention, as well as the compounds relating to performance additives, are considered additive mixtures that are normally used in lubricating compositions in limited amounts to mechanically, physically or chemically stabilize the lubricating compositions. , while the special performance characteristics can be further established by the individual or combined presence of said selected additives.

Additive packages are defined separately in the present invention, as a variety of such additive packages are commercially available and are typically used in lubricant compositions. One of these preferred additive packages that is commercially available is marketed under the name Anglamol6004J®.

However, the individual components contained in the additive packages and / or the compounds further defined herein as so-called performance additives include a greater number of different types of additives, including dispersants, metal deactivators, detergents, extreme pressure (which usually contain boron and / or sulfur and / or phosphorus), antiwear agents, antioxidants (such as hindered phenols, amino antioxidants or molybdenum compounds), corrosion inhibitors, foam inhibitors, demulsifiers, depressants of the flowability, joint swelling agents, friction modifiers and mixtures thereof.

The additive component as the sum of all the additives contained in the lubricant compositions according to the present invention, including also all the additives contained in an additive package or added separately, is present in the lubricant compositions of the present invention in an amount of 0 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 2 to 12% by weight, and more preferably in an amount of 3 to 10% by weight.

Extreme pressure agents include boron and / or sulfur and / or phosphorus containing compounds. The extreme pressure agent can be present in the lubricant compositions in a proportion of 0% by weight to 20% by weight, or from 0.05% by weight to 10% by weight, or from 0.1% by weight to 8%. % by weight of the lubricating composition.

In one embodiment according to the present invention, the extreme pressure agent is a sulfur-containing compound. In one embodiment, the sulfur-containing compound can be a sulfurized olefin, a polysulfide, or mixtures thereof. Examples of the sulfurized olefin include a sulfurized olefin derived from propylene, isobutylene, pentene; an organic sulfide and / or polysulfide, including benzidisulfide; bis- (chlorobenzyl) disulfide; dibutyl tetrasulfide; di-tertiary butyl polysulfide; and sulfurized oleic acid methyl ester, a sulfurized alkylphenol, a sulfurized dipentene, a sulfurized terpene, a sulfurized Diels-Alder adduct, an alkyl sulfenyl N'N-dialkyl dithiocarbamates; or mixtures thereof.

In one embodiment, the sulfur olefin includes a sulfur olefin derived from propylene, isobutylene, pentene, or mixtures thereof.

In one embodiment according to the present invention, the sulfur-containing compound of the extreme pressure agent includes a dimercaptothiadiazole or derivative, or mixtures thereof. Examples of dimercaptothiadiazole include compounds such as 2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof. Hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole oligomers are typically formed by the formation of a sulfur-sulfur bond between 2,5-dimercapto-1,3,4-thiadiazole units to form derivatives or oligomers of two or more of said thiadiazole units. Suitable 2,5-dimercapto-1,3,4-thiadiazole derivative compounds include, for example, 2,5-bis (tertonilidium) -1,3,4-thiadiazole or 2-tertonylidium-5- mercapto-1,3,4-thiadiazole. The number of carbon atoms in the hydrocarbyl substituents of the substituted 2,5-dimercapto-1,3,4-thiadiazole typically includes 1 to 30, or 2 to 20, or 3 to 16. In one embodiment, the dimercaptothiadiazole it may be a thiadiazole functionalized dispersant. A detailed description of the thiadiazole functionalized dispersant is described in paragraphs [0028] to [0052] of International Publication WO 2008/014315.

The thiadiazole functionalized dispersant can be prepared by a process that includes heating, reacting, or complexing a thiadiazole compound with a dispersant substrate. The thiadiazole compound may be covalently linked, complexed with a salt, or otherwise solubilized with a dispersant, or mixtures thereof.

The relative amounts of the dispersant substrate and thiadiazole used to prepare the thiadiazole functionalized dispersant can vary. In one embodiment, the thiadiazole compound is present from 0.1 to 10 parts by weight relative to 100 parts by weight of the dispersant substrate. In other embodiments, the thiadiazole compound is present in greater than 0.1 to 9, or greater than 0.1 to less than 5, or 0.2 to less than 5: to 100 parts by weight of the dispersant substrate. The relative amounts of the thiadiazole compound to the dispersant substrate can also be expressed as (0.1-10): 100, or (> 0.1-9): 100, (as (> 0.5-9): 100 ), or (0.1 to less than 5): 100, or (0.2 to less than 5): 100.

In one embodiment, the dispersant substrate is present in 0.1 to 10 parts by weight relative to 1 part by weight of the thiadiazole compound. In different embodiments the dispersant substrate is present in greater than 0.1 to 9, or greater than 0.1 to less than 5, or about 0.2 to less than 5: to 1 part by weight of the thiadiazole compound. The relative amounts of the dispersant substrate to the thiadiazole compound can also be expressed as (0.1-10): 1, or (> 0.1-9): 1, (as (> 0.5-9): 1 ), or (0.1 to less than 5): 1, or (0.2 to less than 5): 1.

The thiadiazole functionalized dispersant can be derived from a substrate that includes a succinimide dispersant (e.g., N-substituted long chain alkenyl succinimides, typically a polyisobutylene succinimide), a Mannich dispersant, an ester-containing dispersant, a product Condensation of a fatty hydrocarbyl monocarboxylic acylating agent with an amine or ammonia, an alkyl amino phenol dispersant, a hydrocarbyl-amine dispersant, a polyether dispersant, a polyetheramine dispersant, a viscosity modifier containing dispersant functionality ( for example, polymeric viscosity index modifiers containing dispersant functionality), or mixtures thereof. In one embodiment, the dispersant substrate includes a succinimide dispersant, an ester-containing dispersant, or a Mannich dispersant.

In one embodiment according to the present invention, the extreme pressure agent includes a boron-containing compound. The boron-containing compound includes a borate ester (which in some embodiments may also be referred to as a boron epoxide), a boron alcohol, a boron dispersant, a boron phospholipid, or mixtures thereof. In one embodiment, the boron-containing compound can be a borate ester or a boron alcohol. The borate ester can be prepared by reacting a boron compound and at least one compound selected from epoxy compounds, halohydrin compounds, epihalohydrin compounds, alcohols, and mixtures thereof. Alcohols include dihydric alcohols, trihydric alcohols, or higher alcohols, provided that in one embodiment the hydroxyl groups are on adjacent, ie, vicinal, carbon atoms.

Suitable boron compounds for preparing the borate ester include the various forms selected from the group consisting of boric acid (including metabolic acid, orthoboric acid, and tetraboric acid), boric oxide, boron trioxide, and alkyl borates. The borate ester can also be prepared from boron halides.

In one embodiment, suitable borate ester compounds include tripropyl borate, tributyl borate, tripentyl borate, trihexyl borate, triheptyl borate, trioctyl borate, trinonyl borate, and tridecyl borate. In one embodiment, the borate ester compounds include tributyl borate, tri-2-ethylhexyl borate, or mixtures thereof.

In one embodiment, the boron-containing compound is a borated dispersant, typically derived from an N-substituted long chain alkenyl succinimide. In one embodiment, the borated dispersant includes a polyisobutylene succinimide. Borated dispersants are described in more detail in US Patents 3,087,936 and 3,254,025.

In one embodiment, the borated dispersant can be used in combination with a sulfur-containing compound or a borate ester.

In one embodiment, the extreme pressure agent is other than a borated dispersant.

The number average molecular weight Mn (GPC; kg / mol) of the hydrocarbon from which the long chain alkenyl group was derived includes ranges from 350 to 5000, or from 500 to 3000, or from 550 to 1500. The chain alkenyl group long can have a number average molecular weight of 550, or 750, or 950 to 1000.

The N-substituted long chain alkenyl succinimides are borated using a variety of agents including boric acid (eg, metabolic acid, orthoboric acid, and tetraboric acid), boric oxide, boron trioxide, and alkyl borates. In one embodiment, the boring agent is boric acid, which can be used alone or in combination with other boring agents.

The borated dispersant can be prepared by mixing the boron compound and the N-substituted long chain alkenyl succinimides and heating them to a suitable temperature, for example, from 80 ° C to 250 ° C, or from 90 ° C to 230 ° C, or from 100 ° C to 210 ° C, until the desired reaction occurs. The molar ratio of boron compounds to long chain N-substituted alkenyl succinimides can have ranges including 10: 1 to 1: 4, or 4: 1 to 1: 3; or the molar ratio of boron compounds to long chain N-substituted alkenyl succinimides can be 1: 2. Alternatively, the ratio of B moles: N moles (i.e., B atoms: N atoms) in the borated dispersant may be 0.25: 1 to 10: 1 or 0.33: 1 to 4: 1 or 0.2: 1 to 1.5: 1, or 0.25: 1 to 1.3: 1, or 0.8: 1 to 1.2: 1, or approximately 0.5: 1 A inert liquid to carry out the reaction. The liquid can include toluene, xylene, chlorobenzene, dimethylformamide, or mixtures thereof.

In one embodiment, the additive component in the lubricant composition according to the present invention further includes a borated phospholipid. The borated phospholipid can be derived from boronation of a phospholipid (eg, boronation can be carried out with boric acid). Phospholipids and lecithins are described in detail in the Encyclopedia of Chemical Technology, Kirk and Othmer, 3rd edition, in "Fats and Fatty Oils", volume 9, pages 795-831 and in "Lecithins", volume 14, pages 250- 269.

The phospholipid can be any lipid that contains a phosphoric acid, such as lecithin or cephalin, or their derivatives. Examples of phospholipids include phosphatidylcholine, phosphatidylserine, phosphatidylinositol, phosphatidylethanolamine, phosphotidic acid, and mixtures thereof. Phospholipids can be glycerophospholipids, derived from glycerol from the above list of phospholipids. Typically, glycerophospholipids have one or two acyl, alkyl, or alkenyl groups on a glycerol residue. Alkyl or alkenyl groups can contain 8 to 30, or 8 to 25, or 12 to 24 carbon atoms. Some examples of suitable alkyl or alkenyl groups are octyl, dodecyl, hexadecyl, octadecyl, docosanyl, octenyl, dodecyl, hexadecyl, and octadecyl.

Phospholipids can be prepared synthetically or derived from natural sources. Synthetic phospholipids can be prepared by procedures known to those of skill in the art. The naturally occurring phospholipids are often extracted by procedures known in the art. Phospholipids can come from animal or plant sources. A useful phospholipid is derived from sunflower seeds. Phospholipid usually contains between 35% and 60% phosphatidylcholine, between 20% and 35% phosphatidylinositol, between 1% and 25% phosphatidic acid and between 10% and 25% phosphatidylethanolamine, being the percentages by weight on the total phospholipids. The content of fatty acids can be from 20% by weight to 30% by weight of palmitic acid, from 2% by weight to 10% by weight of stearic acid, from 15% by weight to 25% by weight of oleic acid and 40% by weight to 55% by weight of linoleic acid.

In another embodiment, the performance additive in lubricant compositions according to the present invention may include a friction modifier. A friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid that contains said material (s). Friction modifiers, also known as friction reducers, or lubricity agents or oiliness agents, and other agents of this type that change the capacity of base oils, the Formulated lubricating compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface can be effectively used in combination with the base oils or lubricating compositions of the present invention if desired. Friction modifiers can include metal-containing materials or composites, as well as ashless composites or materials, or mixtures thereof. Metal-containing friction modifiers can include metal salts or metal-ligand complexes, where the metals can include alkali, alkaline earth, or transition group metals. Such metal-containing friction modifiers can also have low ash characteristics. Transition metals can include Mo, Sb, Sn, Fe, Cu, Zn, and others. Ligands can include hydrocarbon derivatives of alcohols, polyols, glycerols, partial ester glycerols, thiols, carboxylates, carbamates, thiocarbamates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines, thiazoles, thiazoles, diazoles, diazoles, and dithiazoles other polar molecular functional groups containing effective amounts of O, N, S or P, individually or in combination. In particular, compounds containing Mo, such as Mo-dithiocarbamates, Mo (DTC), Modithiophosphates, Mo (DTP), Mo-amines, Mo (Am), Moalcoholates, Mo -alcoholamides, and the like.

Ashless friction modifiers can also include lubricating materials that contain effective amounts of polar groups, eg, hydroxyl-containing hydrocarbyl base oils, glycerides, partial glycerides, glyceride derivatives, and the like. The polar groups in friction modifiers can include hydrocarbyl groups containing effective amounts of O, N, S, or P, individually or in combination. Other friction modifiers that may be particularly effective include, for example, salts (both ash-containing and ashless derivatives) of fatty acids, fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates, and synthetic hydrocarbyl acids. comparable long chain alcohols, amides, esters, hydroxycarboxylates, and the like. In some cases, organic fatty acids, fatty amines and sulfur fatty acids can be used as suitable friction modifiers.

In one embodiment, the performance additive in the lubricant compositions according to the present invention may include antiwear agents containing phosphorus or sulfur other than the compounds described as an extreme pressure agent of the amine salt of a phosphoric acid ester described above. Examples of the antiwear agent may include a nonionic phosphorus compound (typically compounds having phosphorous atoms with an oxidation state of 3 or 5), a metal dialkyldithiophosphate (typically zinc dialkyldithiophosphates), amine dithiophosphate, ashless dithiophosphates, and a metal mono or dialkyl phosphate (typically zinc phosphates), or mixtures thereof.

The nonionic phosphorus compound includes a phosphite ester, a phosphate ester, or mixtures thereof.

In one embodiment, the performance additive in the lubricant composition according to the present invention may further include at least one antioxidant. Antioxidants retard oxidative degradation of base materials during service. Such degradation can lead to deposits on metal surfaces, the presence of sludge, or an increase in the viscosity of the lubricant. A wide variety of oxidation inhibitors are known to one skilled in the art that are useful in lubricating oil compositions.

Useful antioxidants include hindered phenols. These phenolic antioxidants can be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenolics, which are those that contain a sterically hindered hydroxyl group, and these include those derived from dihydroxy aryl compounds in which the hydroxyl groups are in the o or p position relative to each other. Typical phenolic antioxidants include C6 + alkyl substituted hindered phenols and alkylene-coupled derivatives of these hindered phenols. Examples of such phenolic materials: 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful hindered monophenolic antioxidants may include, for example, propionic 2,6-di-alkylphenolic hindered ester derivatives. Bis-phenolic antioxidants can also be used advantageously in combination with the present invention. Examples of ortho-coupled phenols include: 2,2'-bis (4-heptyl-6-t-butyl-phenol); 2,2'-bis (4-octyl-6-t-butyl-phenol); and 2,2'-bis (4-dodecyl-6-t-butylphenol). Paracoupled bisphenols include, for example, 4,4'-bis (2,6-di-t-butyl phenol) and 4,4'-methylene-bis (2,6-di-t-butyl phenol ).

Among the non-phenolic oxidation inhibitors that can be used are aromatic amine antioxidants, which can be used as such or in combination with phenolics. Typical examples of nonphenolic antioxidants include: alkylated and non-alkylated aromatic amines, such as aromatic monoamines of the formula R8R9R10N, where R8 is an aliphatic, aromatic, or substituted aromatic group, R9 is an aromatic or substituted aromatic group, and R10 is H , alkyl, aryl or R11S (O) xR12, where R11 is an alkylene, alkenylene or aralkylene group, R12 is a higher alkyl group, or an alkenyl, aryl or alkaryl group, and x is 0, 1 or 2. The aliphatic group R8 it may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms. The aliphatic group is a saturated aliphatic group. Preferably, both R8 and R9 are aromatic or substituted aromatic groups, and the aromatic group can be a fused ring aromatic group, such as naphthyl. The aromatic groups R8 and R9 can be attached to other groups such as S.

Typical aromatic amine antioxidants have alkyl substituent groups of at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, aliphatic groups will not contain more than about 14 carbon atoms. General types of amino antioxidants useful in the present compositions include diphenylamines, phenylnaphthylamines, phenothiazines, imidodibenzyl, and diphenylenediamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used. Particular examples of aromatic amine antioxidants useful in the present invention include: p, p'-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenylalphanaphthylamine; and p-octylphenyl-alpha-naphthylamine. Sulfurized alkylphenols and alkali or alkaline earth metal salts thereof are also useful antioxidants.

In one embodiment, the performance additive in lubricant compositions according to the present invention further includes a dispersant. The dispersant may be a succinimide dispersant (e.g., N-substituted long chain alkenyl succinimides), a Mannich dispersant, an ester-containing dispersant, a condensation product of a fatty hydrocarbyl monocarboxylic acylating agent with a amine or ammonia, an alkyl amino phenol dispersant, a hydrocarbyl-amine dispersant, a polyether dispersant, or a polyetheramine dispersant.

In one embodiment, the succinimide dispersant includes a polyisobutylene substituted succinimide, wherein the polyisobutylene from which the dispersant is derived can have a number average molecular weight of 400 to 5000, or 950 to 1600. The succinimide dispersants and their preparation procedures are described in more detail in US Patents 4,234,435 and 3,172,892. Suitable ester-containing dispersants are typically high molecular weight esters. These materials are described in more detail in US Patent 3,381,022.

In one embodiment, the dispersant includes a borated dispersant. Typically, the borated dispersant includes a succinimide dispersant that includes a polyisobutylene succinimide, where the polyisobutylene from which the dispersant is derived can have a number average molecular weight of 400 to 5000. Borated dispersants are described in more detail above within the description of the extreme pressure agent.

Dispersant viscosity modifiers (often referred to as DVMs) are considered additives in the context of the present invention due to their additional functionalization and therefore are not considered viscosity enhancing agents according to the present invention. Dispersant viscosity modifiers include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of maleic anhydride and an amine, an amine-functionalized polymethacrylate, or reacted esterified styrene-maleic anhydride copolymers. with an amine.

As another type of performance additive, corrosion inhibitors can be described as any material (additives, functionalized fluids, etc.) that forms a protective film on a surface that prevents corrosion agents from reacting or attacking that surface with consequent loss of surface material. Protective films can be absorbed onto the surface or chemically bonded to it. The protective films can be constituted by monomolecular species, oligomeric species, polymeric species or mixtures of them. The protective films can be derived from intact corrosion inhibitors, their combined products, or their degradation products, or mixtures thereof. Surfaces that can benefit from the action of corrosion inhibitors can include metals and their alloys (both ferrous and non-ferrous) and non-metals.

Corrosion inhibitors can include various materials that contain oxygen, nitrogen, sulfur, and phosphorus, and can include metal-containing compounds (salts, organometallic, etc.) and non-metal or ashless materials. Corrosion inhibitors may include, but are not limited to, types of additives such as hydrocarbon, aryl, alkyl, arylalkyl, and alkylaryl (neutral, overbasic) versions of detergents, sulfonates, phenates, salicylates, alcoholates, carboxylates, salixarates, phosphites, phosphates, thiophosphates, amines, amine salts, phosphoric acid salts of amines, sulfonic acid salts of amines, alkoxylated amines, etheramines, polyetheramines, amides, imides, azoles, diazoles, triazoles, benzotriazoles, benzothiazoles, mercaptobenzotriazoles , tolyltriazoles (TTZ type), heterocyclic amines, heterocyclic sulfides, thiazoles, thiadiazoles, mercaptothiadiazoles, dimer-captothiadiazoles (DMTD type), imidazoles, benzimidazoles, dithiobenzimidazoles, imidazolines, oxazolines, mannichidyl reactions, products of the tether carbamates, thiocarbamates, dithiocarbamates, polyglycols, etc., or their mixtures.

Corrosion inhibitors are used to reduce the degradation of metal parts that are in contact with the lubricating composition. Suitable corrosion inhibitors include thiadiazoles. Aromatic triazoles, such as toltriazole, are suitable corrosion inhibitors for non-ferrous metals, such as copper.

Metal deactivators include derivatives of benzotriazoles (typically tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkylithiobenzimidazoles, thiadiazoles, or 2-alkylithiobenzothiazoles.

Foam inhibitors can also be advantageously added as performance additives to lubricant compositions according to the present invention. These agents retard the formation of stable foams. Silicones and organic polymers are typical foam inhibitors. For example, polysiloxanes, such as silicone oil, or polydimethylsiloxane, provide foam-inhibiting properties. Other foam inhibitors are copolymers of ethyl acrylate and 2-ethylhexyl acrylate and, optionally, vinyl acetate. Demulsifiers include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.

Pour point depressants include maleic anhydride-styrene esters, or polyacrylamides.

As another performance additive to be used in lubricant compositions according to the present invention, sealant compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or a physical change in the elastomer. Suitable sealant compatibility agents for lubricating compositions include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzylphthalate, for example), and polybutenyl succinic anhydride. These additives can preferably be used in an amount of 0.01 to 3% by weight, more preferably 0.01 to 2% by weight of the total amount of the lubricating composition.

The present invention provides lubricant compositions having excellent low temperature viscosity and very good rheological properties, including shear stability over a wide temperature range. In particular, the lubricant compositions according to the present invention have high permanent shear stability. The lubricant compositions according to the present invention also have very good oxidation stability.

Another preferred lubricant composition according to the present invention, as illustrated in Inventive Examples 3 (IE-3) and 4 (IE-4), is defined as follows:

Another preferred lubricating composition according to the present invention, as illustrated in Inventive Example 5 (IE-5), is defined as follows:

The lubricant compositions according to the present invention can be used in a variety of different applications. Preferred embodiments include the use of the lubricant compositions according to the present invention in light, medium and heavy duty motor oils, industrial motor oils, marine motor oils, automobile motor oils, crankshaft oils, compressor oils, refrigerator oils, hydrocarbon compressor oils, very low temperature lubricating oils and greases, high temperature lubricating oils and greases, cable lubricants, textile machine oils, refrigerator oils, aviation and aerospace turbine lubricants, transmissions, gas turbine oils, spindle oils, turning oils, traction fluids, plastic transmission oils, passenger car transmission oils, truck transmission oils, industrial transmission oils, industrial gear oils, insulating oils , instrument oils, brake fluids, fluids for transmissions, shock absorber oils, oils for heat distribution media, transformer oils, greases, chain oils, lubricants in trace amounts for metal working operations, oil for hot and cold work, oil for fluids of water-based metalworking, pure oil-based metalworking fluid oil, semi-synthetic metalworking fluid oil, synthetic metalworking fluid oil, drilling detergents for soil exploration, hydraulic oils , in biodegradable lubricants or lubricating greases or waxes, chain saw oils, mold release agents, molding fluids, gun and rifle lubricants or watch lubricants and food approved lubricants.

Examples

Procedures

The measurement of the number average molecular weight Mn of the polymers mentioned in the present invention has been carried out using the industrial standard DIN 55672.

The pour point of the lubricating compositions according to the present invention has been determined according to the established industrial standard DIN ISO 3016 (unless otherwise stated).

The different kinematic viscosities of the lubricant compositions according to the present invention have been determined following established industrial standards.

Kinematic viscosity at -30 ° C, 40 ° C and 100 ° C, respectively, is determined according to established industry standard DIN 51562-1 (unless otherwise stated).

The dynamic viscosity is determined according to DIN 51562-1 and is further calculated by multiplying the measured kinematic viscosity by the corresponding density.

The viscosity index has been determined according to the industrial standard DIN ISO 2909 (unless otherwise stated). Shear stability tests have been carried out according to the industrial standard DIN 51350 / KRL / C.

Preparation of carboxylic acid esters

Preparation of a diisononyl adipate (DNA)

a) Dimerization of butene

The dimerization of the butene was carried out continuously in an adiabatic reactor, composed of two subreactors (length: in each case 4 m, diameter: in each case 80 cm) with intermediate cooling at 30 bar. The starting product used was a raffinate II with the following composition:

isobutane 2% by weight

n-butane 10% by weight

isobutene 2% by weight

1-butene 32% by weight

trans-2-butene 37% by weight and

cis-2-butene 17% by weight.

The catalyst used was a material prepared according to DE-A 4339713, composed of 50% by weight of NiO, 12.5% by weight of TiO2, 33.5% by weight of SiO2 and 4% by weight of AhO3, in the form of 5 * 5mm pads. The reaction was carried out with a yield of 0.375 kg of raffinate II per I of catalyst and hour, with a return ratio of the unreacted C4 hydrocarbons returned to the fresh raffinate II of 3, an inlet temperature in the first subreactor of 38 ° C and an inlet temperature in the second subreactor of 60 ° C. The conversion, based on the butenes present in raffinate II, was 83.1%, and the selectivity of octene was 83.3%. Fractional distillation of the reactor discharge was used to separate the octene fraction from the unreacted raffinate II and the high boilers.

b) Hydroformylation and hydrogenation

750 g of the octene mixture prepared according to section A.1 of the examples were reacted for 5 hours batchwise, in an autoclave, with 0.13% by weight of dicobalt octacarbonyl Co2 (CO) s as catalyst, with the addition of 75 g of water, at 185 ° C. and with a syngas pressure of 280 bar at a ratio of H2 to CO in the mixture of 60/40. More material was injected to compensate for the syngas consumption, which resulted in a pressure drop in the autoclave. After releasing the pressure in the autoclave, the reaction discharge, with 10% strength by weight of acetic acid, was oxidatively released from the cobalt catalyst by introducing air, and the organic phase of the product was hydrogenated using Raney nickel at 125 ° C and with a hydrogen pressure of 280 bar for 10 h. The isononanol fraction was separated from the Ce and high-boiling paraffins by fractional distillation of the reaction discharge.

The composition of the isononanol fraction was analyzed by gas chromatography. A specimen was previously trimethylsilylated using 1 ml of N-methyl-N-trimethylsilyltrifluoroacetamide per 100 µl of specimen for 60 minutes at 80 ° C. A Hewlett Packard Ultra 1 separation column, 50 m long and 0.32 mm deep, was used. internal diameter, with a film thickness of 0.2 pm. The injector and detector temperature was 250 ° C, and the oven temperature was 120 ° C. The split was 110 ml / min. The carrier gas used was nitrogen. The inlet pressure was set at 200 kPa. 1 µl of the sample was injected and detected by FID. The compositions determined for the samples by this procedure (percent per area of the gas chromatogram) were as follows

11.0% 1-nonanol

20.8% 6-methyl-1-octanol

20.5% 4-methyl-1-octanol

5.3% 2-methyl-1-octanol

11.0% 2,5-dimethyl-1-heptanol

8.7% 3-ethyl-1-heptanol

6.2% 4,5-dimethyl-1-heptanol

2.9% 2-ethyl-1-heptanol

2.8% 2,3-dimethyl-1-heptanol

3.0% 2-ethyl-4-methyl-1 -hexanol

2.7% 2-propyl-1-hexanol

1.6% 3-ethyl-4-methyl-1 -hexanol

The density of this isononanol mixture was measured at 20 ° C as 0.8326, and the refractive index # 20 as 1.4353. The boiling range at atmospheric pressure was 204 to 209 ° C.

c) Esterification

865.74 g of the isononanol fraction obtained in process step 2 (20% molar excess based on adipic acid) were reacted with 365.25 g of adipic acid and 0.42 g of isopropyl titanate catalyst in a 2 l autoclave in which nitrogen was bubbled (10 l / h) with a stirring speed of 500 rpm and a reaction temperature of 230 ° C. The water formed in the reaction was progressively removed from the reaction mixture with the nitrogen stream. The reaction time was 180 min. The excess nonanol was then distilled off at a reduced pressure of 50 mbar. 1000 g of crude diisononyl adipate were neutralized by stirring for 10 minutes at 80 ° C with 150 ml of 0.5% strength aqueous sodium hydroxide. This gave a mixture of two phases with an upper organic phase and a lower aqueous phase (waste liquor with hydrolyzed catalyst). The aqueous phase was separated and the organic phase was subjected to two more washes with 200 ml of H2O. For further purification, the neutralized and washed diisononyl adipate was stripped using steam at 180 ° C and a reduced pressure of 50 mbar for two hours. The purified diisononyl adipate was then dried for 30 minutes at 150 ° C and 50 mbar by passing a stream of nitrogen (2 L / h) through the material, and then mixed with activated carbon for 5 minutes and filtered with suction through a suction filter using Supra-Theorit 5 filter aid (temperature 80 ° C).

The resulting diisononyl adipate has a density of 0.920 g / cm3 and a refractive index nD20 of 1.4500.

Rheological profile of lubricant compositions at different temperatures

Claims (8)

1. Lubricant composition comprising, based on the total weight of the lubricating composition to. at least 55% by weight of a dicarboxylic acid ester component selected from di-isononyladipate (DNA) and di- (2-ethylhexyl) adipate (DOA), b. 10 to 25% by weight of an ethylene-propylene copolymer, and c. 5 to 20% by weight of a monocarboxylic acid ester, wherein the ethylene-propylene copolymer (b) has a kinematic viscosity according to JIS K 2283 at 100 ° C in the range of 1000 to 2200 mm2 / s. 2. Lubricating composition according to claim 1, wherein the lubricating composition has a kinematic viscosity according to DIN 51562-1 industrial standard of not more than 1600 mm2 / s at -30 ° C and of at least 7.5 mm2 / s at 100 ° C. Lubricant composition according to at least one of the preceding claims, having a viscosity index according to DIN ISO 2909 of at least 160. 4. Lubricant composition according to at least one of the preceding claims, further comprising a base oil component having a kinematic viscosity according to DIN 51562-1 at 100 ° C in the range of 1 to 5 mm2 / s. Lubricant composition according to at least one of the preceding claims, in which the monocarboxylic acid ester is selected from the list consisting of 2-ethylhexylate, 2-ethylhexylcocoate, 2-ethylhexylpalmitate, 2-ethylhexylstearate, 2-ethylhexyltallowate and their mixtures. Lubricating composition according to at least one of the preceding claims, in which the ratio between the dicarboxylic acid ester component and the oligomeric copolymer is in the range of 2: 1 to 19: 1 based on the relative weight of these components in lubricating compositions. Lubricating composition according to at least one of the preceding claims, further comprising an additive component which is present in an amount of 0.1 to 20% by weight of the total lubricating composition. Use of the lubricating composition according to claims 1 to 7 as a vehicle transmission oil, axle oil, industrial transmission oil, industrial gear oil, compressor oil, turbine oil, hydraulic oil or motor oil.