KR100744983B1 - Power transmission fluids with enhanced antishudder durability and handling characteristics - Google Patents

Abstract

Provided are lubricant compositions that have enhanced friction durability and improved μ / v properties on paper, steel and enhanced friction materials, such as carbon fibers, which make minimal consideration to skin sensitivity and related health, stability, and environmental issues. Friction modifiers prepared by reacting a lubricating base oil, aliphatic monoacids such as oleic acid, isostearic acid and polyamines under conditions such that the finished power transmission fluid forms a 1,2-disubstituted imidazoline containing components. Which may further comprise acrylated residue active nitrogen with mono or diacids or anhydrides to obtain friction modifier compositions and handling properties with enhanced friction.

Description

POWER TRANSMISSION FLUIDS WITH ENHANCED ANTISHUDDER DURABILITY AND HANDLING CHARACTERISTICS}

[Brief Description of Drawings]

1 exemplarily graphically shows a comparison between a conventional automatic transmission fluid A and an automatic transmission fluid B according to the invention.

2 is a schematic depicting an apparatus for performing LFW-1 testing.

Background of the Invention

The present application is directed to fluids having improved friction durability and μ / v properties on paper, metal and enhanced friction materials. The fluids described herein can exhibit improved handling properties and improved anti-shudder durability. The present invention includes a device, such as a lubricated power transmission fluid device with the fluid.

 New and enhanced delivery systems have been developed by the automotive industry. Such novel systems often include high energy conditions. Therefore, component protection techniques need to be developed to meet the increasing energy requirements of promoting systems, to promote fuel efficiency, and to extend satisfactory friction conditions at low and high speeds.

New and enhanced delivery systems used in passenger cars and heavy duty vehicles continue to be more sophisticated as vehicle technology advances. The design results from the need for improved vehicle operability, reliability, and fuel efficiency. Vehicle manufacturers worldwide are increasing vehicle warranty periods and service intervals on their vehicles. This means that the transmission and the transmission fluid must be designed to work reliably without maintenance for longer periods of time. In the case of a fluid, this means longer drain intervals. Especially at low temperatures, preparations for improving vehicle operability have been given precise conditions for fluid viscosity at -40 ° C.

For longer drain intervals and more stringent operating conditions, manufacturing increases the conditions of fluid oxidation resistance, requires less change in viscosity with vehicle fuel economy (improved shear stability), and the fluid is provided for the transmission The amount of wear protection has been increased. In order to improve the fuel efficiency of vehicles and reduce energy losses, recent manufacturers have continuously used the clutch as both a wet start clutch or a torque converter clutch. The device requires very precise control of fluid friction.

Constant research on how to improve total vehicle fuel efficiency has identified a torque converter, or fluid coupling, used between the engine and automatic transmission as a relatively large source of energy loss. Since the torque converter is a fluid coupling, it is not as efficient as the solid disc clutch. At any set of operating conditions (engine speed, throttle position, ground speed transmission gear ratio), there is a relative speed difference between the driven and torque converter members. Its relative speed difference represents the lost energy from which heat is dissipated from the torque converter.

One way to improve the total vehicle fuel efficiency used by transmission builders has been to make a torque machine a clutch machine that can "lock" the torque converter. "Locking" means no energy loss in the fluid coupling by eliminating relative motion between the driven members of the drive and torque converters. The "locking" or "lock-up" clutch is very effective for obtaining energy loss at large road speeds. However, when used at low speeds, vehicle operation is rough and engine vibrations are transmitted through the driven train. Rough operation and engine vibration are not allowed to the driver.

The higher the percentage of time that the vehicle can be operated with an interlocked torque converter clutch, the better the fuel efficient vehicle. A further generation of torque converter clutches has been developed to operate in "slipping" or "continuously sliding mode". The device has many names but is generally referred to as a continuous sleeping torque converter clutch. The difference between the device and the lock-up clutch is that they have some relative movement between the driven source and the drive of the torque converter, normally at a relative speed of 50 to 500 rpm. The slow speed of sleeping allows the sleeping clutch to act as a vibration damper for improved vehicle performance. On the other hand, "lock-up" type clutches can only be used at road speeds above about 50 mph, while "sleeping" type clutches can be used at speeds as low as 25mps, which can capture significant energy losses. This is a very interesting feature for vehicle manufacturers.

Another approach to reduce energy loss between the engine and the transmission is to use a wet start clutch. Wet starting clutches are similar to shifting clutches but are designed to handle the full energy of the vehicle. Therefore, this tends to be physically larger than the shifting clutch. However, as a torque converter clutch, it slides continuously to improve overall vehicle driveability and ride comfort.

Continuous sleeping clutches are suitable for all transmission types. Continuous sleeping torque converter clutches and / or wet start clutches are customarily used as transmission types, such as conventional automatic transmissions, continuously variable transmissions (CVTs), manual transmissions, and dual clutch transmissions.

Continuous sleeping clutches, such as continuous sleeping torque converter clutches, impose very stringent friction conditions of the automatic transmission fluid (ATF) used therein. The fluid has a very good friction versus speed relationship, ie the friction should always increase with increasing speed. If friction is reduced at increasing speeds, a self-exciting vibrational state can be provided in the power transmission system. This phenomenon is commonly referred to as "stick-slip" or "dynamic frictional vibration" and manifests itself as a low speed vibration or "shudder" in a vehicle. Clutch vibration can be a major problem for the driver. Fluids that operate the vehicle without vibration or shudder are said to have good "anti-shudder" properties. When a fluid is new, it not only has a good friction versus speed relationship, but must also maintain its friction for the life of the fluid and this can be the life of the transmission. The lifetime of the anti-shudder performance of a vehicle is generally referred to as "anti-shudder durability".

Lubricating continuous continuously variable transmissions and sleeping clutch systems with steel push belts or chain drive variants is not a simple matter. This represents a need for exceptional evidence of good paper-on-steel friction for sleeping clutches and steel-on-steel friction for variators. Solving the need to meet the above conditions further needs to provide the durability of the friction performance required over a wide range of temperatures at which the fluid operates. Therefore, the friction modifier system must provide very precise control of steel-on-steel friction and paper-on-steel friction over a wide range of operating conditions, such as a wide range of temperatures.

Previous achievements include US Pat. No. 5,750,476; 5,811,377; 5,840,662; 5,840,663; EP 0393769 B2; EP 0877784 B1; As well as those described elsewhere, including those described in US Pat. No. 5,395,539, which is free of imidazole.

Despite the previous achievements, there remains a need for compositions and methods that can industrially address the need. Identifying any of the compounds described below that can be easily formulated for a power transmission fluid, such as an automatic transmission, and providing a unique solution that provides the desired properties, such as those that extend the anti-shudder durability of the fluid.

Summary of the Invention

Aspects of the present invention may exhibit enhanced friction durability and μ / v properties, in particular positive μ / v curves, and maintain high static capacity during the expected service life on paper, steel and increased friction materials such as carbon fibers. An improved power transmission fluid having what is possible.

Another aspect of the invention provides a lubricating composition that gives minimal consideration to skin sensitivity and related health, safety, and environmental issues.

In an aspect of the present invention, there is provided a method and composition for improving a power transmission fluid, in particular an automatic transmission fluid.

In an embodiment of the invention, friction prepared by reaction of an aliphatic monoacid such as oleic acid, isostearic acid and a polyamine under conditions for forming a mixture of a lubricating base oil, a 1,2-disubstituted imidazoline containing constituents A fluid composition comprising a modifier and any other performance enhancing additive. Acrylation of mono or diacids or anhydrides with residue active nitrogen yields friction modifier ("FM") compounds with enhanced friction and handling properties.

In one aspect of the invention, the fluid is produced under the conditions of producing a reaction product of an aliphatic carboxylic acid with a polyamine, in particular a compound comprising 1,2-disubstituted imidazolines, for example comprising a compound represented by the formulas Reaction products obtained under include:

[Formula I]

And

[Formula II]

Wherein R ₁ is a group consisting of C ₃ to C ₃₀ straight or branched alkyl, alkenyl, aryl, or heteroatom derivatives thereof or propylene isobutylene and a high olefin having terminal, intermediate and vinylidene double bonds Oligomers / polymers derived from can be selected from the group consisting of hydrocarbyl groups, and hetero derivatives thereof, where "n" can range from 0 to 5); And / or the reaction product is post-treated with a secondary carboxylic acid or carboxylic acid derivative.

Fluids formulated as power transmission fluids may include effective amounts of one or more oil-soluble ashless dispersants such as succinimide dispersants, succinic ester dispersants, succinic acid ester-amide dispersants, Mannich base dispersants, phosphorylation and / or borated forms thereof. .

Fluid formulations according to aspects of the present invention may be added to commercially available additive additives such as, for example, air expulsion additives, antioxidants, corrosion inhibitors, foam inhibitors, metallic detergents, organophosphorus compounds, suture-sealants. swell), viscosity index improvers, EP additives used in conventional amounts.

Fluids according to aspects of the present invention may be formulated for use as industrial gears or automotive gears. On the vehicle side, the fluid may include a power transmission device such as one or more electronically controlled converter clutches, sleeping torque converters, lock-up torque converters, starting clutches and one or more shifting clutches; Or for use as a transmission using a differential device. For example, it includes the incorporation of automatic transmissions, including lock-up and dual clutches, semi-automatic transmissions, automated manual transmissions, and continuous continuously variable transmissions (CVTs). Post-treated reaction products, one or more ashless dispersants, and any one or more other performance additives, antifoams, anti-wear agents, corrosion inhibitors, EP additives, metallic cleaners, organophosphorus compound (s), green inhibitors, suture expanders, viscosities Fluids comprising friction modifiers composed of index improvers can be used in automatic transmissions.

The present invention relates to a method for improving the stability against oxidative decomposition, ie, to maintain a relatively constant kinetic friction coefficient in a power transmission fluid by incorporating an effective amount of friction modifier (s) represented by formulas (I) to (VI) below into the fluid. It includes such additional implementations as promoting periods.

Detailed Description of the Invention

Vehicles that meet demanding consumer demands for durability and all performance within the vehicle system. One of the most important systems is the power transmission system ("transmission"), which transmits the power produced by the car engine with wheels. This is one of the most complex systems in the vehicle and also one of the most expensive to diagnose, repair or replace. Among them, the transmission generally includes a clutch having a plate, a torque converter, and a plurality of gears that change the power transmitted to the wheels by varying the gear ratio.

Discriminating consumers primarily demand high performance, low maintenance costs (high fuel economy between services), and extended life expectancy. However, with the advent of new transmission technology, previously approved old standard performance is now a problem.

The advent of electronically controlled converter clutch (ECCC) designs, as well as advances in vehicles with continuous continuously variable transmissions (CVT) and aerodynamic body designs, are small transmissions that tend to operate at higher energy densities and higher operating temperatures. Made a car with. The change has challenged lubricant suppliers to formulate automatic transmission fluids with new and unique performance characteristics including better torque and friction durability.

  Original equipment manufacturers (OEMs) required automatic transmission fluids with frictional properties that could meet ECCC, CVT, and other design needs while maintaining significant performance in the anti-wear field.

For extended transmission fluid life and high endurance durability and improved durability of kinetic friction coefficients, we have long felt the way to meet the needs of OEM automotive designers and suppliers, and an efficient way to solve the problems associated with automatic transmissions. There is a need.

The present invention has improved durability in lubricating fluids, for example, extended anti-shudder durability, by providing automatic transmission fluids that can exhibit good performance over a long period of time, without significant degradation, and exhibit sufficient kinetic friction coefficients. It is a response to the long felt need for improved stability to oxidation.

 Friction Modifiers can be used in automatic transmission fluids that reduce friction between surfaces (eg, structures of torque converter clutches or shifting clutches) at low sliding speeds. The result is a friction versus speed (μ-v) curve with a positive slope, which in turn applies a soft clutch and "stick-slip" action (e.g., shudder, noise, and coarse movement). Minimize.

Increasing desirable properties such as stability against oxidation with reduced vibrations with anti-shudder durability and coefficient of kinetic friction are complex and pose problems. In contrast to the increased amount of identifiable solution of conventional friction modifiers in the power transmission fluid, the increased concentration may actually reduce the total friction level represented by the fluid. Decreasing the coefficient of friction below any minimum value is not required because the capacity of the clutch in the transmission can be reversed, so that the clutch slips more when the transmission is in operation. Clutch wear increases and the clutch is spoiled by unwanted slips.

In order to deal with these and other objections in the prior art, the fluids according to the invention, like essential components, are represented by fatty carboxylic acids (ROOH) and polyamines (PA), for example represented by the formulas I and / or II. Post-secondary with a secondary carboxylic acid or carboxylic acid derivative to obtain a reaction product, and / or a compound represented by any of Formula III-VI, under conditions sufficient to produce a mixture of 1,2-disubstituted imidazolines And the reaction product treated. The composition of the final reaction product can be determined by the molar ratio of carboxylic acid and polyamine.

Generalized structures I to VI illustrate and illustrate typical friction modifiers for use in various fluid implementations in accordance with the present invention. The friction modifier may be formed under the conditions as described below.

The reaction product of the first acid (R ₁ COOH) and the polyamine (s) can produce a mixture containing a compound represented by formula (I) and a compound represented by formula (II). A molar excess is used for the polyamine of the first organic acid.

[Formula I]

And

[Formula II]

The molar ratio of the first carboxylic acid to the polyamine can vary depending on the desired composition of the reaction product. In general, the molar ratio may suitably be selected in the range of about 1.0 to about 2.0, and as further examples, may range from about 1.2 to about 1.6. In addition, the molar ratio of carboxylic acid to polyamine may be about 4: 3. For example, at low molar ratios, the composition may consist predominantly of the compound (s) represented by formula (I), while at high molar ratios, the composition predominantly possesses the compound (s) represented by formula (II). Can be configured. The molar ratio may correspond to the excess of the first carboxylic acid relative to the polyamine.

Representative primary acids are those that provide an R ₁ moiety. The R ₁ moiety may be independent of one another, and may be C ₃ to C ₃₀ linear or branched alkyl, alkenyl or aryl groups or heteroatom derivatives thereof, such as, for example, alkyl having a hetero atom. . The present invention therefore contemplates, in one implementation thereof, using a combination of first acids. Representative moieties are fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, dodecenoic acid, hexadecenoic acid, oleic acid, iso-oleic acid, linoleic acid, arachidic acid, or any combination thereof It includes. The R ₁ group may be incorporated with hydrocarbyl aromatic acids such as 4-dodecylbenzoic acid, 2-hexadecylnicotinic acid, and 4-polyisobutyl acid. Suitable friction modifiers include those derived from the reaction of polyamines such as triethylene tetramin with fatty acids exemplified by oleic or isostearic acid.

Heteroatom derivatives of R ₁ may include O, S, N, and / or P, as will be understood by one skilled in the art.

Representative polyamines can be linear or branched as implied by compounds represented by Formulas I-VI (n = 0-5). Exemplary classifications of polyethylene amines include internal repeating units of-(CH ₂ CH ₂ NH) _x- (wherein x may be an integer from 1 to 10, and in further examples x may be an integer from 1 to 6). Include. The polyamine is represented by the formula H ₂ N- (CH ₂ CH ₂ NH) _x -CH ₂ CH ₂ NH ₂ , where x is 1, it is diethylene triamine, when x is 2, it is triethylene tetramine When x is 3, it is tetraethylene pentamine, which is one of the suitable polyamines. Commercial mixtures of highly polyamines are also suitable. Amino groups are aromatic or aliphatic ring structures such as o-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylamine, melamine, or 1,8-diamino-p-mentane, other moieties. May be part of or combined.

For example, suitably elevated temperatures in the range of about 120 ° C. to about 180 ° C., such as about 150 ° C., for example when x = 2, of the selected first acid, such as C ₁₇ H ₃₃ COOH, and a suitably selected polyamine. The reaction for a sufficient time at a molar ratio of about 4 to about 3 at a temperature, such as about 5 to about 20 hours, or, as a further example, about 12 to 16 hours, is carried out by the reaction of the compound (s) represented by the formulas (I) and (II) , R ₁ is C ₁₇ H ₃₅ Moieties). The relative ratio of the compound represented by the formula (I) described to the compound represented by the formula (II) described may in principle be about 2: 1. Other rains may be possible. The relative ratio of compound (s) represented by formula (I) to compound (s) represented by formula (II) can be determined by the ratio of carboxylic acid to polyamine.

Embodiments of the invention are fluids, such as power transmission fluids or concentrates, which include one or more compounds represented by Formula (I) and / or Formula (II).

Post-treatment (or reaction product) of a mixture comprising at least one second organic acid (R ₂ COOH) and the compound (s) represented by formulas (I) and / or (II) may be carried out. The second organic acid can be obtained with a second mixture (or second reaction product) comprising the compound (s) represented by formula (III) and the compound (s) represented by formula (IV) in an amount sufficient to acrylate all reactive nitrogen atoms. .

[Formula III]

And

[Formula IV]

The level of acrylated may generally be about 0% to about 100% and further examples may be, for example, about 50% to about 100%.

An exemplary second acid is to provide an R ₂ moiety. The R ₂ moiety may be independent of another and may be C ₃ to C ₃₀ linear or branched alkyl, alkenyl, or aryl, or heteroatom derivatives thereof, such as alkyl having a heteroatom as an example. . Therefore it is also planned as a combination of the first acid of the present invention. Representative moieties are from fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, iso-stearic acid, dodecenoic acid, hexadecenoic acid, oleic acid, iso-oleic acid, linoleic acid, arachidic acid, or Any mixture thereof. R ₂ groups may be incorporated with hydrocarbyl aromatic or heteroaromatic acids such as 4-dodecylbenzoic acid, 2-hexadecylnicotinic acid, or 4-polyisobutyl benzoic acid, and the like.

Heteroatom derivatives of R ₂ include O, S, N, and / or P atoms as those skilled in the art will appreciate.

In an embodiment of the present invention a fluid, such as a power transmission fluid or concentrate, contains one or more compounds represented by structures III and IV.

Post-treatment of a mixture comprising an excess of substituted anhydrides such as substituted succinic acids or anhydrides with the compounds represented by formulas (I) and (II) can be carried out. The amount of substituted organic acid or anhydride may be an amount sufficient to acrylate all or part of the reactive nitrogen to produce a mixture of compound (s) represented by Formula (V) and a compound represented by Formula (VI).

[Formula V]

And

[Formula VI]

The level of acrylated may generally be about 0% to about 100% and further examples may range from about 50% to about 100%, for example.

Representative substituted organic acids and anhydrides correspond to the R ₃ and R ₄ moieties. The R ₃ and R ₄ moieties may be independent of each other and may reflect the use of a combination of suitable reactants. R ₃ and R ₄ groups have H, —OH, —OR, —COOH, —SH, —SR, straight chain, branched alkyl, alkenyl radicals or propylene, isobutylene and terminal, internal, and vinylidene double bonds It may be selected from the group consisting of oligomeric or polymer type hydrocarbyl groups of high olefins. The molecular weight of R ₃ and R ₄ can vary and can be as large as 1000 amu. R represents an alkyl or alkenyl group having up to 30 carbon atoms, for example 16 to 22 carbon atoms, in a linear, branched, or cyclic form.

Thus, representative substituted organic acids and anhydrides include low molecular weight, oil-insoluble acids or anhydrides. Examples include succinic anhydride, phthalic anhydride, tartaric acid, citric acid, maleic acid, and mercaptosuccinic acid.

    Suitable post-treatment reactants are succinic anhydrides prepared by isomerization of linear α-olefins with acid catalysts followed by reaction with maleic anhydride. Such methods of preparation are described, for example, in US Pat. No. 6,548,458; 5,620,486; 5,393,309; 5,021,169; US 4,958034; 4,234,435; 3,676,089; 3,361,673; And 3,172,892 and European Patent 0623631 B1.

An embodiment of the present invention is a fluid, such as a power transmission fluid or concentrate, which contains one or more compound (s) represented by Formulas V and / or VI.

The friction modifier (s) described above idealizes to some extent compositions that are incapable of incorporating crosslinking products and by-products due to vibration at the acrylate level.

Fluids according to the present invention include any combination of the above compounds and may contain one or more compounds from those represented by formulas (I)-(VI). Suitable mixtures of compounds are, for example, mixtures of compounds represented by formula I, mixtures of compounds represented by formula II, mixtures of compounds represented by formula III, mixtures of compounds represented by formula IV, mixtures of compounds represented by formula V, A mixture of a compound represented by VI, a mixture of compound (s) represented by formula I and a compound (s) represented by formula II, a mixture of compound (s) represented by formula III and a compound represented by formula IV, a compound represented by formula V ( And mixtures of compounds (s) represented by formula (VI), mixtures of compounds from among those represented by formulas I, II, III, and IV, mixtures of compounds from those represented by formulas I, II, V, and VI It includes.

Suitable combinations of reactants and reagents are selected to produce a friction modifier composition comprising a compound wherein R ₁ is oleyl or isostearyl and R ₃ and / or R ₄ are isomerized α-olefin derived hydrocarbyl groups. Can be. In addition, R ₃ and / or R ₄ may comprise a moiety of polyisobutylene or a C ₁₆ to C ₂₂ isomerized α olefin having a molecular weight of about 200 to about 950 amu. Compounds represented by formulas (I)-(VI) are described in US Pat. Nos. 3,254,025; 3,502,677; 4,686,054; And 4,857,214, respectively, and may be treated with inorganic acids such as phosphoric acid, phosphorous acid, sulfuric acid, and borated and malitized.

The level of said component in the finished oil-containing power transmission fluid may range from about 0.01 to about 10% (weight%). Suitable ranges are about 0.1 to about 5.0 weight percent. For example, the component may comprise a mixture of compounds represented by Formula V and Formula VI.

Dispersant (Soluble)

In aspects of the present invention, the fluid may comprise one or more oil-soluble type dispersants such as succinimide dispersants, succinic ester dispersants, succinic acid ester-amide dispersants, Mannich base dispersants, phosphorylation and / or borated forms thereof Can be. The total dispersant content of the fluids, such as power transmission fluids, according to the invention can vary from 0.1 to 20% by weight. As a further example, a suitable range can be about 2.0 to about 7.0 weight percent.

Oil-soluble dispersants may include ashless dispersants such as succinimide dispersants, Mannich base dispersants, and polymerizable polyamine dispersants. Hydrocarbyl-substituted succinic acid acrylates are used to prepare hydrocarbyl-substituted succinimides. Hydrocarbyl-substituted succinic acrylates include, but are not limited to, hydrocarbyl-substituted succinic acid, hydrocarbyl-substituted succinic anhydride, hydrocarbyl-substituted succinic halides (particularly acid fluorides and acid chlorides), and hydrocarbyl-it includes substituted compounds-esters and a lower alcohol of the substituted succinic acid (e.g., comprises less than or equal to the number 7 carbon atoms), that is, carboxylic acid hydrochloride which can serve as an acrylic agent Bill .

Hydrocarbyl substituted acrylates are prepared by reacting maleic anhydride with chlorinated polyolefins or polyolefins of appropriate molecular weight. Similar carboxylic acid reactants can be used to prepare the acrylates. The reactants include, but are not limited to, acidic halides and lower aliphatic esters, maleic acid, fumaric acid, malic acid, tartaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride , Dimethylmaleic anhydride, ethylmaleic acid, dimethylmaleic acid, hexylmaleic acid and the like.

The molecular weight of the olefin can vary depending on the intended use of the substituted succinic anhydride. Typically, the substituted succinic anhydride will have hydrocarbyl of about 8 to about 500 carbon atoms. However, substituted succinic anhydrides used as lubricant dispersants will typically have hydrocarbyl of about 40 to about 500 carbon atoms. As the olefins used to prepare the substituted succinic anhydrides may comprise mixtures of different molecular weight constituents as a result of the polymerization of low molecular weight olefin monomers such as ethylene, propylene, and isobutylene, This can be more accurately referred to as the number average molecular weight (Mn).

The molar ratio of maleic anhydride to olefin can vary widely. For example, about 5: 1 to about 1: 5, or, for example, about 1: 1 to about 3: 1. Olefins such as polyisobutylene having a number average molecular weight of about 500 to about 7000, or as further examples, at least about 800 to about 3000 and ethylene-alpha-olefin copolymers, maleic anhydride is a stoichiometric excess, for example For example from about 1.1 to about 3 moles of maleic anhydride per mole of olefin. Unreacted maleic anhydride can be evaporated from the resulting reaction mixture.

Polyalkenyl succinic anhydrides can be converted to polyalkyl succinic anhydrides using conventionally decreasing conditions such as catalytic hydrogenation. Suitable catalysts for catalytic hydrogenation are palladium on carbon. In addition, polyalkenyl succinimides can be converted to polyalkyl succinimides using similar reducing conditions.

Polyalkyl or polyalkenyl substituents on succinic anhydrides used in the present invention are generally derived from polyolefins, which are polymers or copolymers of mono-olefins, in particular 1-mono-olefins such as ethylene, propylene, and butylene . The mono-olefins used are about 2 to about 24 carbon atoms, or further, about 3 to about 12 carbon atoms. Other suitable mono-olefins include propylene, butylene, in particular isobutylene, 1-octene, and 1-decene. Polyolefins made from such mono-olefins include polypropylene, polybutene, polyisobutene, and polyalphaolefins made from 1-octene and 1-decene.

In some embodiments, ashless dispersants may include one or more alkenyl succinimide groups of amines having one or more primary amino groups capable of forming imide groups. Alkenyl succinimides can be formed by conventional methods, such as by heating an amine comprising one or more primary amino groups with an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester. Alkenyl succinic anhydrides can be readily prepared by heating a mixture of polyolefin and maleic anhydride at about 180 ° C-220 ° C. The polyolefin can be a polymer or copolymer of lower mono-olefins such as ethylene, propylene, isobutene, etc., having a number average molecular weight of about 300 to about 3000 as measured by gel permeation chromatography (GPC). have.

Amines that can be used to form ashless dispersants include any having one or more primary amino groups and / or one or more hydroxyl groups that can react to form imide groups and one or more additional primary or secondary amino groups. Representative examples include: N-methyl-propanediamine, N-dodecylpropanediamine, N-amino propyl-piperazine, ethanolamine, N-ethanol-ethylenediamine, and the like.

Suitable amines may include alkylene polyamines such as propylene diamine, dipropylene triamine, di- (1,2-butylene) triamine, and tetra- (1,2-propylene) pentamine. Further examples include ethylene polyamines which may be represented by the formula H ₂ N (CH ₂ CH ₂ NH) _n H, wherein n may be an integer from about 1 to about 10. This includes mixtures thereof where n is the average of the mixture and includes: ethylene diamine, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine ( PEHA), etc. The ethylene polyamine has a primary amine at each end to form mono-alkenylsuccinimide and bis-alkenylsuccinimide. Commonly used ethylene polyamine mixtures include branched and cyclic species such as N-aminoethyl piperazine, N, N'-bis (aminoethyl) piperazine, N, N'-bis (piperazinyl) ethane, and the like. Small amounts may be included. The commercial mixture may have a rough overall composition in the range of the corresponding diethylene triamine to tetraethylene pentamine. The molar ratio of polyalkenyl succinic anhydride to polyalkylene polyamine can be from about 1: 1 to about 3.0: 1.

In some embodiments, the ashless dispersant comprises two or more of the foregoing materials and includes an unsubstituted polycarboxylic acid with polyethylene polyamines, such as triethylene tetramine or tetraethylene pentamine, and polyolefins of suitable molecular weight such as polyisobutene Or products of reactions of hydrocarbon substituted carboxylic acids or anhydrides prepared by the reaction of anhydrides such as maleic anhydride, maleic acid, fumaric acid, and the like.

Also suitable polyamines for preparing the dispersants described herein are N-arylphenylenediamines, such as N-phenylphenylenediamine, such as N-phenyl-1,4-phenylenediamine, N-phenyl-1,3- Phenylenediamine, and N-phenyl-1,2-phenylenediamine; Aminothiazoles such as aminothiazole, aminobenzothiazole, aminobenzothiadiazole, and aminoalkylthiazole; Aminocarbazole; Aminoindoles; Aminopyrrole; Amino-indazolinone; Aminomercaptotriazole; Aminoperimidine; Aminoalkyl imidazoles such as 1- (2-aminoethyl) imidazole, 1- (3-aminopropyl) imidazole; And aminoalkyl morpholines such as 4- (3-aminopropyl) morpholine. Such polyamines are described in more detail in US Pat. Nos. 4,863,623 and 5,075,383. The polyamines can provide additional advantages such as anti-wear and antioxidancy to provide the final product.

Additional polyamines useful for forming hydrocarbyl-substituted succinimides include polyamines having one or more primary or secondary amino groups and one or more tertiary amino groups in the molecule, as described in US Pat. Nos. 5,634,951 and 5,725,612. do. Examples of suitable polyamines are N, N, N ", N" -tetraalkyldialkylenetriamines (two terminal tertiary amino groups and one central secondary amino group), N, N, N ', N "-tetraalkyltrialkyl Lentetramine (one terminal tertiary amino group, two internal tertiary amino groups and one terminal primary amino group), N, N, N ', N ", N'"-pentaalkyltrialkylenetetramine (one A terminal tertiary amino group, two internal tertiary amino groups and one terminal secondary amino group), tris (dialkylaminoalkyl) -aminoalkylmethane (three terminal tertiary amino groups and one terminal primary amino group), and the like Wherein the alkyl groups are the same or different and typically contain no more than about 12 carbon atoms each, and each may contain from about 1 to about 4 carbon atoms In a further example, the alkyl group is a methyl and / or ethyl group. Polyamine reactants of this type may be selected from the group consisting of dimethylaminopropylamine (DM APA) and N-methyl piperazine.

Hydroxyamines suitable for use in the present invention include compounds, oligomers or polymers containing one or more primary or secondary amines capable of reacting with hydrocarbyl-substituted succinic acids or anhydrides. Hydroxyamines suitable for use in the present invention include aminoethylethanolamine (AEEA), aminopropyl diethanolamine (APDEA), ethanolamine, diethanolamine (DEA), partially propoxylated hexamethylene diamine (e.g. HMDA -2PO or HMDA-3PO), 3-amino-1,2-propanediol, tris (hydroxymethyl) aminomethane, and 2-amino-1,3-propanediol.

The molar ratio of amine to hydrocarbyl-substituted succinic acid or anhydride may range from about 1: 1 to about 3.0: 1. Another example of a molar ratio of amine to hydrocarbyl-substituted succinic acid or anhydride can be from about 1.5: 1 to about 2.0: 1.

The preceding dispersants may also be treated with, for example, maleic anhydride and boric acid as described, for example, in US Pat. No. 5,789,353, or nonylphenol, formaldehyde, for example, as described in US Pat. No. 5,137,980. And post-treatment dispersants prepared by treating the dispersant with glycoic acid.

Mannich base dispersants have at least one aliphatic aldehyde containing from about 1 to about 7 carbon atoms (particularly formaldehyde and derivatives thereof), and polyamines (particularly polyalkylene polyamines), which typically have long chain alkyl substituents in the ring. May be a reaction product of an alkyl phenol. For example, the Mannich base ashless dispersant may be formed by condensation of about 1 mole ratio of chain hydrocarbon-substituted phenol with about 1 to about 2.5 moles of formaldehyde and about 0.5 to about 2 moles of polyalkylene polyamine.

The hydrocarbon source for the preparation of the Mannich polyamine dispersant may be derived from a sufficiently saturated petroleum fraction and an olefin polymer, such as a polymer of mono-olefins having about 2 to about 6 carbon atoms. Hydrocarbon sources are generally, for example, at least 40 carbon atoms and in further examples, contain at least 50 carbon atoms to provide sufficient utility to the dispersant. Olefin polymers having GPC number average molecular weights between about 600 and about 5,000 are suitable for reasons of easy reactivity and low cost. However, polymers of polymer can also be used. Particularly suitable hydrocarbon sources are isobutylene polymers made from a mixture of isobutene polymers and raffinate I streams.

Suitable Mannich base dispersants are Mannich base ashless dispersants formed by condensation of about 1 to about 2.5 moles of formaldehyde and about 0.5 to about 2 moles of polyalkylene polyamine with about 1 mole ratio of long chain hydrocarbon-substituted phenols. Can be.

Polymeric polyamine dispersants suitable as ashless dispersants are polymers comprising a base amine group and an oil soluble group (eg, a suspension alkyl group having about 8 or more carbon atoms). The materials are described by various monomers such as decyl methacrylate, vinyl decyl ether, or by interpolymers formed from relatively high molecular olefins with aminoalkyl acrylates and amino alkyl acrylamides. Examples of polymerizable polyamine dispersants are described in US Pat. No. 3,329,658; 3,449,250; 3,493,520; 3,519,565; 3,666,730; 3,687,849; And 3,702,300. The polymerizable polyamine comprises a hydrocarbyl polyamine, wherein the hydrocarbyl group consists of the polymerization product of the raffinate I stream and isobutene described above. PIB-amines and PIB-polyamines are also used.

Processes for preparing the ashless dispersant described above are known to those skilled in the art and reported in the patent literature. For example, the synthesis of various ashless dispersants of the previous type is described in the following patents: US Pat. No. 2,459,112, incorporated by reference; 2,962,442, 2,984,550; 3,036,003; 3,163,603; 3,166,516; 3,172,892; 3,184,474; 3,202,678; 3,215,707; 3,216,936; 3,219,666; 3,236,770; 3,254,025; 3,271,310; 3,272,746; 3,275,554; 3,281,357; 3,306,908; 3,311,558; 3,316,177; 3,331,776; 3,340,281; 3,341,542; 3,346,493; 3,351,552; 3,355,270; 3,368,972; 3,381,022; 3,399,141; 3,413,347; 3,415,750; 3,433,744; 3,438,757; 3,442,808; 3,444,170; 3,448,047; 3,448,048; 3,448,049; 3,451,933; 3,454,497; 3,454,555; 3,454,607; 3,459,661; 3,461,172; 3,467,668; 3,493,520; 3,501,405; 3,522,179; 3,539,633; 3,541,012; 3,542,680; 3,543,678; 3,558,743; 3,565,804; 3,567,637; 3,574,101; 3,576,743; 3,586,629; 3,591,598; 3,600,372; 3,630,904; 3,632,510; 3,632,511; 3,634,515; 3,649,229; 3,697,428; 3,697,574; 3,703,536; 3,704,308; 3,725,277; 3,725,441; 3,725,480; 3,726,882; 3,736,357; 3,751,365; 3,756,953; 3,793,202; 3,798,165; 3,798,247; 3,803,039; 3,804,763; 3,836,471; 3,862,981; 3,872,019; 3,904,595; 3,936,480; 3,948,800; 3,950,341; 3,957,746; 3,957,854; 3,957,855; 3,980,569; 3,985,802; 3,991,098; 4,006,089; 4,011,380; 4,025,451; 4,058,468; 4,071,548; 4,083,699; 4,090,854; 4,173,540; 4,234,435; 4,354,950; 4,485,023; 5,137,980; And Re 26,433.

Examples of suitable ashless dispersants are borated dispersants. Borated dispersants are ashless dispersants having basic nitrogen and / or one or more hydroxyl groups in the molecule, such as succinimide dispersants, succinamide dispersants, succinic ester dispersants, succinic ester-amide dispersants, Mannich base dispersants, or hydro It can be formed by boronetizing (carboring) a carbyl amine or polyamine dispersant.

Methods that can be used to boronate various types of ashless dispersants described above are described in US Pat. No. 3,087,936; 3,254,025; 3,281,428; 3,282,955; 2,284,409; 2,284,410; 3,338,832; 3,344,069; 3,533,945; 3,658,836; 3,703,536; 3,718,663; 4,455,243; And 4,652,387.

The borated dispersant includes a high molecular weight dispersant treated with boron such that the borated dispersant comprises about 2% by weight or less of boron. As another example, the borated boric acid agent may comprise up to about 0.8% by weight of boron. As a further example, the borated dispersant may comprise about 0.1 to about 0.7 weight percent of boron. As another example, the borated dispersant may comprise about 0.25 to about 0.7 weight percent of boron. As a further example, the borated dispersant may comprise about 0.35 to about 0.7 weight percent of boron. Dispersants can be dissolved in oils of suitable viscosity for easy operation. Without any diluent oil added, a given weight percentage can be understood for pure dispersants.

Dispersants may be further treated with organic acids, anhydrides, and / or aldehyde / phenol mixtures. The process can be enhanced, for example, with an elastomeric seal. The borated dispersant may further comprise a mixture of borated dispersants. As a further example, the borated dispersant may include a nitrogen-containing dispersant and / or may be free of phosphorus.

Other additives

 The power transmission fluid may also include conventional additives of the type used in automatic transmission fluid formulations and gear lubricants. The additives include, but are not limited to, antifoaming agents (foam inhibitors), antioxidants, anti-rust additives, anti-wear additives, colorants, corrosion inhibitors, dispersants, metal deactivators, metallic detergents, organophosphorus compounds, Pour Point Depressants, Suture expander and / or viscosity index enhancer. Additives are generally C.V. Smalheer et al., Lubricant Additive, p. 1-11 (1967) and US Pat. No. 4,105,571, and others. Additional additives include those that are commercially available.

Antifoam

In some embodiments, the fluid according to the present invention comprises bubble inhibitor (s) which is another component suitable for use of the composition. Foam inhibitors can be selected from silicones, polyacrylates, surfactants, and the like. The amount of antifoam of the transmission fluid formulation described herein can range from about 0.001% to about 0.5% by weight relative to the total weight of the formulation. As a further example, the antifoaming agent may be present in an amount from about 0.01% to about 0.1% by weight.

Antioxidant additives

In some embodiments, antioxidant compounds are included in the composition. Antioxidants include phenolic antioxidants, aromatic amine antioxidants, sulfurized phenolic antioxidants, and organic phosphites, and the like. Examples of phenolic antioxidants include 2,6-di-tert-butylphenol, liquid mixtures of tertiary butylated phenols, 2,6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis ( 2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl6-tert-butylphenol), mixed methylene-crosslinked polyalkyl phenols, and 4,4'-thiobis (2 -Methyl-6-tert-butylphenol), N, N'-di-sec-butyl-phenylenediamine, 4-isopropylaminodiphenylamine, phenyl-α-naphthyl amine, phenyl-α-naphthyl amine , Diarylamines such as diphenylamine and ring-alkylated diarylamines such as ring-alkylated diphenylamines. Examples include sterically hindered tertiary butylated phenols, bisphenols and cinnamic acid derivatives and combinations thereof. The amount of antioxidant in the transmission fluid composition described herein may be about 0.01 to about 10 weight percent based on the total weight of the fluid formulation. As a further example, the antioxidant may be present in an amount from about 0.1% by weight to about 2.0% by weight.

Anti-rust additive

Fluid compositions according to the invention may comprise one or more rust or corrosion inhibitors. The material includes monocarboxylic acids and polycarboxylic acids. Examples of suitable monocarboxylic acids are octanoic acid, decanoic acid and dodecanoic acid. Suitable polycarboxylic acids are prepared from such acids as dimer acids and trimer acids such as tall oil fatty acids, oleic acid, linoleic acid and the like. Other types of rust inhibitors useful are alkenyl succinic and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenyl succinic acid, tetrapropenyl succinic anhydride, tetradecenyl succinic acid, tetradecenyl succinic anhydride, hexadecenyl succinic acid, Hexadecenylsuccinic anhydride and the like. Also useful are half esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in alkenyl groups with alcohols such as polyglycols. Other suitable rust or corrosion inhibitors include ether amines; Acidic phosphoric acid; Amines; Polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; Imidazoline; Aminosuccinic acid or derivatives thereof and the like. Materials of this type are commercially available. Mixtures of the above rust or corrosion inhibitors may be used. The amount of rust inhibitor in the transmission fluid formulations described herein may range from about 0.01 to about 5.0 weight percent relative to the total weight of the formulation.

Anti-wear additive

The antiwear properties of the finished fluid can optionally be modified by the addition of one or more additional antiwear agents. Additional antiwear agents include those comprising phosphorus-containing antiwear agents such as phosphoric acid, organic esters of phosphorous acid or amine salts thereof. For example, the phosphorus-containing anti-wear agent may include one or more dihydrocarbyl phosphites, trihydrocarbyl phosphites, dihydrocarbyl phosphates, trihydrocarbyl phosphates, any anti analogs thereof, and any amines thereof. Salts may be included. As a further example, the phosphorus-containing antiwear agent can include one or more dibutyl hydrogen phosphites and amine salts of dibutyl hydrogen phosphite sulfide.

The phosphorus-containing antiwear agent may be present in an amount sufficient to provide about 50 to about 500 ppm weight of phosphorus in the power transmission fluid. As a further example, the phosphorus-containing antiwear agent may be present in an amount sufficient to provide about 150 to about 300 ppm weight of phosphorus in the power transmission fluid.

The power transmission fluid may comprise from about 0.01% to about 5.0% by weight of the phosphorus-containing antiwear agent. As a further example, the power transmission fluid may comprise from about 0.2% to about 0.3% by weight of the phosphorus-containing antiwear agent. By way of example, about 0.1% to about 0.2% by weight of the power transmission fluid dibutyl hydrogen phosphate or 0.3% to about 0.4% by weight of the amine salt of dibutyl hydrogen phosphate may be included.

Colorant (die)

In some embodiments, the fluids according to the present invention may include colorants to provide fluids of detectable properties. In general, Azo classification dies such as those described in the color index of "the American Association of textile Chemists and Colorists and the Society of Dyers and Colourists (U.K.)". Solvent Red 24 or C.I. Solvent Red 164 is used. For automatic transmission fluids, Automatic Red Dye is preferred. Dye is present in a very minimal amount, such as about 200 to about 300 ppm in the finished fluid.

Corrosion inhibitor

In some embodiments, the fluid according to the present invention may include a copper corrosion inhibitor. Suitable copper corrosion inhibitors include compounds such as thiazoles, triazoles, and thiadiazoles. Examples of such compounds are benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercapto benzothiazole, 2,5-dimercapto-1,3,4-thia Diazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazole, 2, 5-bis (hydrocarbylthio) -1,3,4-thiadiazole, and 2,5-bis (hydrocarbyldithio) -1,3,4-thiadiazole. Suitable compounds are 1,3,4-thiadiazole, many of which are available as commercial articles, and also 1,3,5-thiadiazole such as 2,5-bis (alkyldithio) -1,3,4-thiadia Sol and triazoles such as tolyltriazole. Regarding dialkyl thiadiazoles for the addition of corrosion inhibitors, previous additives are used in the present invention to enhance extreme pressure and anti-wear properties (when used in combination with relatively high levels of sulfided fatty oil as indicated herein). It is being used at a much lower treatment level than the previous one. 1,3,4-thiadiazole is generally synthesized from hydrazine and carbon dioxide by known methods. See, eg, US Pat. No. 2,765,289; 2,749,311; 2,760,933; 2,850,453; 2,910,439; 3,663,561; 3,862,798; And 3,840,549.

Other friction modifier

 Friction Modifiers Fluids according to the present invention containing a friction modifier compound represented by Formula I-VI, or any combination of the foregoing friction modifiers, may optionally include other friction modifiers, including those known in the art. . Examples of such other friction modifiers are alkylated or ethoxylated fatty amines, amide glycerol esters and different imidazolines (or derivatives thereof).

Other friction modifiers are compounds such as aliphatic amines or ethoxylated aliphatic amines, ether amines, alcoholylated ether amines, aliphatic fatty acid amides, acrylated amines, aliphatic carboxylic acids, aliphatic carboxylic esters, polyol esters, aliphatic carboxyl esters- Amides, imidazolines, tertiary amines, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates, and the like, wherein aliphatic groups typically comprise one or more carbon atoms to render the compound suitable do. As a further example, aliphatic groups may contain about 8 or more carbon atoms. Also suitable are aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia or primary amines.

Succinimides can include the reaction product of succinic anhydride and ammonia or primary amines. The alkenyl group of alkenyl succinic acid may be a short chain alkenyl group, for example an alkenyl group which may contain about 12 to about 36 carbon atoms. In addition, the succinimide may comprise about C ₁₂ to about C ₃₆ aliphatic hydrocarbyl succinimide. As a further example, the succinimide can comprise about C ₁₆ to about C ₂₈ aliphatic hydrocarbyl succinimide. As a further example, the succinimide can comprise about C ₁₈ to about C ₂₄ aliphatic hydrocarbyl succinimide.

Succinimides can be prepared from succinic anhydride and ammonia as described in European Patent Application No. 0 020 037, incorporated by reference. In some embodiments, the succinimide can include one or more compound (s) having the structure:

[Wherein Z may be of the structure:

Wherein R ¹ or R ² may both be hydrogen or not, and R ¹ and R ² are independently straight or branched chain hydrocarbon groups containing from about 1 to about 34 carbon atoms, which is the total carbon of R ¹ and R ² About 11 to about 35 atoms, X is an amino group derived from ammonia or a primary amine); Additionally or alternatively, the parent succinic anhydride is obtained by isomerizing an olefinic double bond of a linear α-olefin or mixture thereof comprising maleic acid, anhydride, or ester with about 12 to about 36 carbon atoms. It can be formed by reacting with an internal olefin to obtain a mixture of internal olefins. The reaction can include molar amounts such as ammonia and can be carried out at elevated temperatures at which water is removed.

One group of other friction modifiers is N-aliphatic hydrocarbyl-substituted diethanol amines, wherein the N-aliphatic hydrocarbyl-substituents are free of acetylenic unsaturation and have a range of about 14 to about 20 carbon atoms. At least one straight aliphatic hydrocarbyl group.

Suitable examples of other suitable friction modifier systems consist of a combination of one or more N-aliphatic hydrocarbyl-substituted diethanol amines and one or more N-aliphatic hydrocarbyl-substituted trimethylene diamines, wherein the N-aliphatic Hydrocarbyl-substituents are one or more straight-chain aliphatic hydrocarbyl groups free of acetylenic unsaturation and having a range of about 14 to about 20 carbon atoms. Further details regarding such friction modifier systems are set forth in US Pat. Nos. 5,372,735 and 5,441,656.

Still other suitable examples of other friction modifier systems include (i) acyclic hydroxides wherein the same or different hydroxyalkyl groups each contain about 2 to about 4 carbon atoms and the aliphatic group contains about 10 to about 25 carbon atoms. At least one di (hydroxyalkyl) aliphatic tertiary amine that is a hydroxyalkyl group and (ii) a hydroxyalkyl group containing about 2 to about 4 carbon atoms and an aliphatic group containing about 10 to about 25 carbon atoms It is based on a combination of one or more hydroxyalkyl aliphatic imidazolines that are carbyl groups. For further details on the friction modifier system, the reference will be US Pat. No. 5,344,579.

Another suitable group of other friction modifiers include polyolesters such as glycerol monooleate (GMO), glycerol monolaurate (GML), and the like.

Other friction modifiers are described, for example, in European Patent Publications 877784B1, 856042, and 988357; U.S. Patent Nos. 5,750,476 and 5,942,472; And PCT patent publication WO 97/14772 (April 24, 1997), and others.

Generally, in a composition implementation, the composition, such as the power transmission fluid or the additive package, may be included up to about 5 weight percent and as a further example, from about 0.01 to about 3 weight percent of one or more of the other, additives, friction modifiers. May be included.

Metallic cleaner

Any metallic cleaner may optionally be included in the power transmission fluid of the present invention or in an additive package. Suitable metallic detergents may include overbased salts or oil soluble neutrals of alkali or alkaline earth metals with one or more of the following acidic substances (or mixtures thereof): (1) sulfonic acids, (2) carboxylic acids, (3) Organic phosphoric acid characterized by salicylic acid, (4) alkyl phenol, (5) alkyl sulfide alkyl phenol, and (6) one or more direct carbon-phosphorus linkages. The organic phosphoric acid may be used to convert olefin polymers (e.g., polyisobutylene having a molecular weight of about 1,000) into phosphating agents such as phosphorus trichloride, phosphorus sulfide, phosphorus pentasulphide, phosphorus trichloride and sulfur, white phosphorus and sulfur halides, or And those prepared by treatment of phosphorothio chlorides.

Suitable salts may include neutral or overbased salts of magnesium, calcium, or zinc. As a further example, suitable salts may include magnesium sulfonate, calcium sulfonate, zinc sulfonate, magnesium phenate, calcium phenate, and / or zinc phenate. See, eg, US Pat. No. 6,482,778. The salt may be used alone or in combination with another additive. For example, suitable calcium salts can, in principle, be included in combination with other additives, such as organic phosphates in power transmission fluids, additive packages, or concentrates.

Oil-soluble neutral metal-containing detergents are those detergents which contain a stoichiometrically equivalent amount of metal relative to the amount of acidic moiety present in the detergent. Thus, neutral detergents generally have a low basicity when compared to their overbased counterparts. Acidic materials used to form the detergents include carboxylic acid salicylic acid, alkylphenols, sulfonic acids, sulfided alkylphenols and the like.

The term “oversalted” in the context of metallic cleaners is used when referring to metal salts in which the metal is present in stoichiometric amounts greater than organic radicals. Commonly used methods of preparing overbased salts include heating the mineral oil of the acid at a temperature of 50 ° C. with a stoichiometric excess of metal neutralizers such as metal oxides, hydroxides, carbonates, bicarbonates or sulfides and filtering the resulting product. Include. The use of "promoters" to assist in the incorporation of excess metals in the neutralization step is known. Examples of compounds useful as promoters include phenolic materials such as phenol, naphthol, alkyl phenols, thiophenols, sulfided alkylphenols, and condensation products of phenolic materials with formaldehyde; Alcohols such as methanol, 2-propanol, octanol, ethylene glycol, stearyl alcohol, and cyclohexylhexyl alcohol; And amines such as aniline, phenylene diamine, phenothiazine, phenyl-beta-naphthylamine, and dodecylamine. Particularly efficient methods of preparing basic salts include the excess of basic alkaline earth metal neutralizers and the mixing of one or more alcohol promoters with an acid and the carbonation of the mixture at elevated temperatures, for example between 60 ° C and 200 ° C.

Examples of suitable metal-containing cleaners include, but are not limited to, neutral and overbased salts of such materials, such as neutral sodium sulfonate, overbased sodium sulfonate, sodium carboxylate, sodium salicylate, sodium phenate, Sodium sulfide, lithium sulfonate, lithium carboxylate, lithium salicylate, lithium phenate, lithium sulfide phenate, magnesium sulfonate, magnesium carboxylate, magnesium salicylate, magnesium phenate, magnesium sulfide , Calcium sulfonate, calcium carboxylate, calcium salicylate, calcium phenate, calcium sulfide, potassium sulfonate, potassium carboxylate, potassium salicylate, potassium phenate, potassium sulfide phenate, zinc sulfo , Zinc carboxylate, zinc salicylate, zinc phenate, and zinc sulfide It includes. Further examples include hydrolyzed phosphosulfide olefins having about 10 to about 2,000 carbon atoms or aliphatic-substituted phenolic compounds and / or hydrolyzed phosphosulfated alcohols having about 10 to about 2,000 carbon atoms. Lithium, sodium, potassium, calcium, and magnesium salts. Further examples include lithium, sodium, potassium, calcium, and magnesium salts of aliphatic carboxylic acids and aliphatic substituted cycloaliphatic carboxylic acids and many other similar alkali and alkaline earth metal salts of oil soluble organic acids. In addition, mixtures of neutral or overbased salts of two or more different alkali and / or alkaline earth metals may be used. Likewise, neutral and / or overbased salts of two or more different acids can also be used.

As is well known, overbased metal cleaners are generally considered to include overbased amounts of inorganic bases in the form of microdispersants or colloidal suspensions. The term "soluble" when applied to a metal cleaner does not have to be strictly, completely or actually useful to the term, in the presence of inorganic salts, but when the cleaner is mixed into the base oil, it is as if they are complete and all soluble in oil As shown, it includes the metal cleaner to behave. Overall, the various metallic cleaners mentioned above are sometimes referred to as neutral, basic, or overbased alkali metal or alkaline earth metal-containing organic acid salts.

Methods of preparing oil-soluble neutral and overbased metallic detergents and alkaline earth metal-containing cleaners are well known to those skilled in the art and are extensively reported in the patent literature. See, for example, US Pat. No. 2,001,108; 2,081,075; 2,095,538; 2,144,078; 2,163,622; 2,270,183; 2,292,205; 2,335,017; 2,399,877; 2,416,281; 2,451,345; 2,451,346; 2,485,861; 2,501,731; 2,501,732; 2,585,520; 2,671,758; 2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,695,910; 3,178,368; 3,367,867; 3,496,105; 3,629,109; 3,865,737; 3,907,691; 4,100,085; 4,129,589; 4,137,184; 4,184,740; 4,212,752; 4,617,135; 4,647,387; And 4,880,550.

     The metallic detergents used in the present invention can be made useful if the borated neutral and / or overbased alkali of alkaline earth metal containing detergents is required. Methods for preparing boronated metallic cleaners are described, for example, in US Pat. No. 3,480,548; 3,679,584; 3,829,381; 3,909,691; 4,965,003; And 4,965,004.

Whereas an effective amount of the metallic detergent is used to enhance the advantages of the present invention, typically the effective amount is about 0.01 to about 5.0 weight percent of the finished fluid, further examples of about 0.05 to about 3.0 weight% of the finished fluid It can be a range.

Organic phosphorus  additive

When formulated as a power transmission fluid and concentrate, or as an additive package, the compositions of the present invention may include organic phosphates. By way of example, the organic phosphate has the structure

R ₁ -X _2- (: X ₁ ) (R ₂ X ₃ ) -XR ₅ (wherein R ₁ and R ₂ independently represent substituted or unsubstituted alkyl, aryl, alkylaryl or 1 to 24 carbon atoms) Having cycloalkyl and X, X ₁ , X ₂ and X ₃ may independently be sulfur or oxygen R ₁ and R ₂ may also contain substituted heteroatoms and, in addition to carbon and hydrogen, for example chlorine, Can be sulfur, oxygen or nitrogen; R ₅ is derived from a reactive olefin and is -CH ₂ -CHR-C (: O) OR ₆ ; -CH ₂ -CR ₇ HR ₈ ; or R ₉ -OC (: O) CH ₂ -CH--C (: O) OR ₁₀ , wherein R is equal to H or R ₁ , R ₆ , R ₇ , R ₉ , R ₁₀ is equal to R ₁ and R ₈ is phenyl or alkyl or alkenyl Substituted phenyl moiety, which moiety has 6 to 30 carbon atoms).

Suture expanding agent

In some embodiments, the fluid according to the present invention comprises a transmission fluid composition selected from a suture expanding agent, such as oil soluble diester, oil soluble sulfone, and mixtures thereof. In general, the most suitable diesters are, C ₈ - to ₁₃ alkanol adipates, Ajay rate, and sebacate (or mixtures thereof), and C ₄ -C ₁₃ alkanols include phthalate (or mixtures thereof). Mixtures of two or more types of diesters (eg, dialkyl adipates and dialkyl azelates, etc.) may be used. Examples of such materials are n-octyl, 2-ethylhexyl, isodecyl, and tridecyl diesters of azelaic acid, sebacic acid, and adipic acid, and n-butyl, isobutyl, pentyl, hexyl, heptyl, of phthalic acid, Octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl diesters.

Other esters which can generally give equivalent performance are polyol esters. Suitable sulfone suture expanding agents are described in US Pat. Nos. 3,974,081 and 4,029,587. Typically the product is used at a level ranging from about 0.1% to about 10.0% by weight in the finished transmission fluid. As a further example, it may be prepared in an amount of about 0.25% by weight to about 1.0% by weight.

Suitable suture expanding agents are oil soluble dialkyl esters of (i) adipic acid, (ii) sebacic acid, or (iii) phthalic acid. Adipate and sebacate will be used in amounts ranging from about 1.0 to about 15.0 weight percent in the finished fluid. In the case of phthalates, the level in the transmission fluid will be in the range of about 1.5 to about 10.0 weight%. In general, larger molecules of adipate, sebacate or phthalate, “bigger” will be the processing speed within the previous range.

Viscosity Index Additives

Fluid composition embodiments of the present invention will include one or more viscosity index enhancers. Since the fluid composition is used as a fluid transmission or gear lubricant composition, suitable viscosity index additives include any conventional viscosity index improver. In general, exemplary classifications of viscosity index additives are polyisoalkylene compounds and polymethacrylate compounds, and the like. Examples of suitable polyisoalkylene compounds for viscosity index improvers include polyisobutylene having an average molecular weight range of about 700 to about 2,500. Embodiments will include mixtures of one or more viscosity index enhancers of the same or different molecular weight. Suitable viscosity index improvers will include styrene-maleic acid esters, poly alkylmethacrylates, and olefin copolymer viscosity index improvers. Dispersants and dispersants-antioxidants Viscosity index improvers, as well as mixtures of previous products may also be used.

Additive Package-Thinner

When the friction modifier compound represented by any of Formulas I-VI, or any mixture of such compounds, is provided in an additive package (sometimes called a concentrate), the concentrate is easily formulated, soluble in components, and additive package. Suitable carrier diluents added to the transfer to. Diluent oils need to be compatible with other components, including base oils and additive packages. The additive package may comprise a large amount of additive consisting of an effective amount of one or more friction modifier (s) represented by formulas (I) to (VI), and may include small amounts of diluent oil, and, optionally, other compatible compatible additives. . For example, diluents, although widely used, may be present in the concentrate in amounts of about 5 to about 20%. Generally speaking, somewhat less diluents are preferred for low transportation costs and throughput rates.

The additives used in the formulation of the compositions used in the present invention may be combined with the base oil individually or in various sub-combinations. However, additive concentrates (ie , additives plus diluents, such as hydrocarbon solvents), are suitable for blending all the components involved. The use of additive concentrates, when in the form of additive concentrates, can benefit from mutual compatibility by the combination of member elements. The use of concentrates also reduces blending time and reduces the likelihood of blending errors.

Finished product and base oil

Finished power transmission fluids according to the present invention are typically (but not always required) in a small amount of additive packages represented by one or more of Formulas I, II, III, IV, V and / or VI, with large amounts of base oil and efficient addition levels. Formulated.

In one embodiment, the power transmission fluid composition is formulated to include a fluid comprising a large amount of base oil and one or more fluid modifiers shown in small but effective formulas (I)-(VI). Exemplary power transmission fluids may contain from about 1.0% to about 25% by weight of an additive composition containing a fluid composition according to the present invention.

Suitable base oils for use in the transmission fluid composition formulations according to the invention can be selected from any synthetic or natural or mixtures thereof. Natural oils include mineral lubricating oils such as liquid petroleum oils and mineral lubricating oils of the solvent treated or acid-treated paraffinic, naphthenic or mixed paraffinic-naphthenic type, as well as animal and vegetable oils (eg caster oil, lard). Oil).

     Oils derived from coal or shale are also suitable. The base oil typically has a viscosity at 100 ° C., for example about 2 to about 15 cSt and, as a further example, about 2 to about 10 cSt. In addition, oils derived from gas-to-liquid processes are also suitable.

Synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers, etc.); Polyalphaolefins such as poly (1-hexene), poly- (1-octene), poly (1-decene), and the like and mixtures thereof; Alkylbenzenes (eg , dodecylbenzene, tetradecylbenzene, di-nonylbenzene, di- (2-ethylhexyl) benzene, etc.); Polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); Alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof.

Alkylene oxide polymers and interpolymers and derivatives thereof, wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic principles that can be used. The oil may contain ethylene oxide or propylene oxide, alkyl and aryl ethers of the polyoxyalkylene polymer (eg, methyl-polyisopropylene glycol ether with an average molecular weight of about 1000, an average molecular weight of about 500-1000 Diphenyl ether of polyethylene glycol having, diethyl ether of polypropylene glycol having an average molecular weight of about 1000-1500 and the like) or mono- and polycarboxylic esters thereof, for example acetic acid ester, mixed C _3-8 Illustrated by the above oils prepared via the polymerization of fatty acid esters, or C ₁₃ oxo of tetraethylene glycol.

Another class of synthetic oils that may be used is dika with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Esters of leric acids (e.g. , phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid , Alkenyl malonic acid, and the like). Specific examples of such esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, Complex esters formed by reacting didecyl phthalate, diecosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, 1 mole sebacic acid with 2 mole tetraethylene glycol, and 2 mole 2-ethylhexanoic acid do.

Esters useful as synthetic oils also include those prepared from C ₅ to C ₁₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like. do.

Thus, the base oil used that can be used to prepare the transmission fluid composition described herein can be selected from any base oil in Group I-V as specified in the "the American Petroleum Institute (API) Base Oil Interchangeability Guidelines".

The base oil group is as follows.

Base oil group ¹ Sulfur (% by weight) Saturation (% by weight) Viscosity index  I group ＞ 0.03  And / or <90 80 to 120 Group II ≤0.03  And  ≥90 80 to 120 III group ≤0.03  And  ≥90 ≥120 IV group    All polyalphaolefins (PAO) V group  Any other not included in group I-IV

I-III are mineral oil base stocks Group ^1.

As stated above, the base oil may be poly-alpha-olefin (PAO). Typically, poly-alpha-olefins are derived from monomers having about 4 to about 30, or about 4 to about 20, or about 6 to about 16 carbon atoms. Examples of useful PAOs include those derived from octene, decene, mixtures thereof, and the like. PAOs may have a viscosity of about 2 to about 15, or about 3 to about 12, or about 4 to about 8 cSt at 100 ° C. Examples of PAOs are 4 cSt poly-alpha-olefins at 100 ° C., 6 cSt poly-alpha-olefins at 100 ° C., and mixtures thereof. Mixtures of the foregoing poly-alpha-olefins and mineral oils can be used.

The base oil may be an oil derived from a Fischer-Tropsch synthetic hydrocarbon. Fischer-Tropsch synthetic hydrocarbons are prepared from synthesis gas containing H ₂ and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require additional processing for use as base oil. For example, hydrocarbons can be hydroisomerized using the process described in US Pat. No. 6,103,099 or 6,180,575; hydrocracked and hydroisomerized using the process described in US Pat. No. 4,943,672 or 6,096,940; Dewaxed using the process described in US Pat. No. 5,882,505; Or US Pat. No. 6,013,171; 6,080,301; Or hydroisomerized and dewaxed using the process described in 6,165,949.

Crude, refined, and refined oils may be used as the base oil of the type of neutral natural or synthetic described above, as well as any mixture of two or more of the foregoing. Crude oil is obtained directly from natural or synthetic sources without further purification. For example, the shale oil obtained directly from the distillation operation, the petroleum oil obtained directly from the primary distillation or the ester oil obtained from the esterification and used without further treatment may be crude oil. Refined oils are similar to crude oils except that they are further treated with one or more purification steps to improve one or more properties. Many such purification techniques such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like are known to those skilled in the art. The refined oil is obtained by a process similar to that used to obtain refined oils applied to refined oils already in use. The rerefined oils are also additionally treated by techniques that are directly known for the removal and removal of additives, impurities, and products from which the products are known and often used as recovered and reprocessed oils.

In arbitrarily selecting any additive, the selected component (s) are soluble or stable dispersed in the additive package and the finished automatic transmission fluid (“ATF”) composition, the other components of the composition must be compatible, and It is important to ensure that the composition does not conflict with the performance properties of the composition, such as extreme pressure, anti-wear, friction, anti-shudder, viscosity and / or shear stability, which are required or required for use in the finished composition. Generally, the auxiliary addition component is used in oil in small amounts sufficient to improve the performance properties and properties of the base fluid. Thus, the amount will vary with respect to the above factors as viscosity characteristics of the base fluid used, required viscosity characteristics in the finished fluid, service conditions indicated by the finished fluid and performance characteristics in the finished fluid.

Generally speaking, however, the general concentrations of additional components in the base fluid (% by weight not shown) have been exemplarily described.

The additive is formulated into the base oil in sufficient amounts to provide its expected performance. Representative effective amounts are shown as follows:

Ingredient Weight%

Dispersants 1-20

Viscosity Index Enhancer 0.1-25

Antioxidants 0.01-10

Corrosion Inhibitor 0.01-2

Detergents and Rust Inhibitors 0.01-5

Suture Expanding Agent 0.1-10

Defoamer 0.001-0.1

Anti-wear agents 0.01-0.5

Other Friction Modifiers 0.01-5

Lubrication Base Oil Level

It will be appreciated that the individual components used may be formulated separately in the base fluid or, if necessary, in various sub-combinations. In general, the specific order of the blending process is not critical. Moreover, the components can be formulated in the form of a separate solution in the diluent. However, when simplifying the blending operation, reducing the likelihood of blending errors, and taking advantage of the compatibility and solubility characteristics obtained by the total concentrate, it is desirable to blend the additional ingredients used in the form of the concentrate.

The additive concentrate may formulate all additional ingredients and, if necessary, combine them in an amount such that a portion of the base oil ingredients produces a finished fluid consistent with the concentrations described above. In most cases, the additive concentrate will include one or more diluents, such as light mineral oil, to facilitate the formulation and handling of the concentrate. Thus, concentrates containing up to 50% by weight or more of one or more diluents and solvents can be used, and the solvents provided are not present in amounts that would interfere with low and high temperature and flash point characteristics and performance of the finished power shear fluid composition. In this regard, the additive component used according to the present invention is selected and appropriate that the additive concentrate or package formula formulated from the component may have a flash point of about 170 ° C. or higher, using the ASTM D-92 test procedure. Can be adjusted in proportion.

Power transmission fluids of embodiments of the present invention are formulated to provide enhanced extreme pressure for applications where metal-to-metal contacts are produced at high pressures, eg, over 2 GPa. The fluid is suitable for automatic and manual transmissions such as step automatic transmissions, continuous continuously variable transmissions, automated manual transmissions, and dual clutch transmissions. Metal-to-metal contact High pressures, such as those found in automatic transmissions, for example those in which the fluid does not have sufficient properties, including extreme pressure protection features, can cause damage to the transmission portion. The power transmission fluid composition described herein has improved performance characteristics. In addition, the power transmission fluids herein are also suitable for electrically controlled converter clutches, sleeping torque converters, lock-up torque converters, starting clutches, and / or one or more shifting clutches. The transmission includes 4-, 5-, 6-, and 7-speed transmission and continuous continuously variable transmissions (chain, belt, or disc type). It can be used for gear applications, such as industrial gear applications and automotive gear applications. The gear-type is not limited and can be spur, spiral bevel, helical, planetary and hypoid. (hypoid) gears. It is used as a shaft, transfer case and the like. In addition it is also useful for metalworking applications.

The so-called LFW-1 test involves measuring the friction between rotating steel rings against a stationary block with important friction materials at a given load and temperature. Test cycles include acceleration and deceleration modes between zero and a maximum speed of 0.5 m / sec. The X- and Y-axes in the graph of FIG. 1 represent the velocity and coefficient of friction, respectively. The end-point of the curve near zero is considered to be the static friction coefficient (μ _sta ), while the midpoint (the highest velocity) is considered to be the kinetic friction coefficient (μ _dyn ). Surprisingly, the fluid according to the invention shows a reduced change (delta) in the coefficient of kinetic friction (μ _d ) between the new and aged conditions compared to conventional fluids. When used as a power transmission fluid, it can be mentioned that samples with μ _s / μ _d values greater than 1 show a problem with a shudder. For example, fresh oil μ _s / μ _d in the rugged, robust range (~ 0.9) with improved (high) coefficient of kinetic friction seen in the aging phase (FM 8,11,12,13,14 in Table 1). fluids of the present invention having a value is μ _s / μ _d this can be seen the low delta. The smaller the delta μ _s / μ _d between the new and the aging, the better is the friction endurance, and if μ _d increases, this may change more efficient power transmission acceptance in the mode of motion over time.

As shown in FIG. 1, when the LFW1 test is performed on a sample heated at 170 ° C. for 296 hours under an air velocity of 10 L / min, the kinetic friction coefficient of the conventional formulation A versus the power transmission fluid B according to the present invention There is little total change.

The frictional advantages of the use of the compositions described herein are illustrated in FIG. 1, which schematically illustrates the LFW-1 friction test comparing new and old oils. Oil A contains oleic acid / TEPA-derived bisacrylamide, while Oil B contains oleic acid / TETA-derived imidazoline reacted with 750 molecular weight PIBSA. Both friction modifiers ("FM") are at a level that provides 950 ppm of nitrogen to the finished fluid.

The fluid according to the invention can be formulated for use in a power transmission fluid, such as a power transmission device comprising an ATF in a transmission. An aspect of the invention is a transmission. Exemplary transmissions are described in "" Transmission and Driveline Design "SAE Paper Number SP-108, Society of Automotive Engineers, Warrendale PA 1995; ["Design of Practices: Passenger Car Automotive Transmmisions", The Third Edition, SAE Publication # AE-18, Society of Automotive Engineers, Warrendale PA 1994); And "Automotive Transmission Advancements", SAE Paper Number SP-854, Society of Automotive Engineers, Warren.

Aspects of the present invention provide a power delivery fluid that provides as a fluid modifier (s) a fluid containing at least one compound represented by Formula (I), (II), (III), (IV), (V) or (VI), or a mixture of any of the above formulas. It is a transmission. For example, suitable mixtures may include compounds represented by formula (I) and compounds represented by formula (II), III, IV, V or VI. Transmission implementations include belt, chain, or disc continuous continuously variable transmissions, 4-, 5-, 6- or 7-speed automatic transmissions, manual transmissions, dual clutch transmissions.

A further aspect of the invention is a vehicle comprising an engine and a transmission, a transmission comprising the power transmission fluid described above. The vehicle may contain a differential, and thus in another embodiment includes a differential comprising a lubricant containing a fluid composition as described above. Vehicles include, without limitation, trucks, automobiles, and some mechanized farm equipment such as tractors or reapers.

EXAMPLE

Exemplary compositions suitable for use in the practice of the present invention are shown in the following examples, all parts and percentages being by weight unless otherwise specified.

Example 1

The reaction of triethylenetetramine (TETA) with isostearic acid was carried out in a 2L three-necked round bottom flask equipped with a pressure equilibrated addition funnel, a distillation condenser, and a mechanical stirrer. To stirred isostearic acid (405.3 g), TETA (153.0 g) was added dropwise at 75 ° C. The addition reaction was continued slowly below 100 ° C. until the reaction no longer exothermic. After addition of the remaining amine, carefully vacuumed (28 Hg) and gradually increased the temperature to 150 ° C. The mixture was stirred under vacuum for 19 h. The reaction was expected to form 44.9 g of water. A total of 48.2 g of volatile material was collected in a dry ice trap.

In the following analysis, the above results for the product were obtained: TAN (D-664) 3.1 mg KOH / g; TBN (D-2869) 262.8 mg KOH / g; KV 100 20.22 cSt; N: 10.97% (Calc'd: 11.41%). IR (cm ^-1 ): 1660, 1613, 1459, 1248, 1004, 726.

Example 2

Example 1 (67.2 g), diluent oil (76.2 g) and C _20-24 alkyl succinic anhydride (87.5 g) (Dixie Chemical Company) were charged to a 500 mL round bottom flask equipped with a distillation condenser and a mechanical stirrer. . The mixture was stirred at 100 ° C. for 1 h under vacuum (28 Hg). Analysis of the resulting product is given below: TAN (D-664) 31.1 mg KOH / g; TBN (D-2869) 37.6 mg KOH / g; N: 3.18% (Calc'd: 3.38%). IR (cm- ¹ ): 1771, 1705, 1649.

Example 3

Example 1 (55.33 g), diluent oil (55.91 g) and a reaction product of 200 molar weight PIBSA (56.29 g) with an activity of 3.34 meq / g were reacted under the conditions described in Example 2. Analysis of the resulting product is as follows: TAN (D-664) 28.8 mg KOH / g; TBN (D-2869) 43.5 mg KOH / g; N: 3.61% (Calc'd: 3.68%). IR (cm- ¹ ): 1778, 1705, 1642.

Example 4

Table 1 shows the LFW-1 results for fresh and aged oils. An embodiment from the broad composition described above of the present invention was used to measure the following friction modifiers in the LFW-1 friction test shown in Table 1. Data is plotted in FIG. 1.

Table 1 shows examples of a number of oil-containing fluid formulations according to the present invention that provide good new oil friction properties (μ _s / μ _d <about 1.0) that undergo very little change after oxidation compared to conventional formulations. .

In Table 1, OA is oleic acid; ISO is isostearic acid; TETA is triethylene tetramine; C _20-24 -ASA is alkyl succinic anhydride, wherein the alkyl group is an isomerized form of a mixture of C ₂₀ to C ₂₄ alpha-olefins. PIBSA refers to polyisobutylene succinic anhydride and the 200 MW, 350 MW, and 750 MW designations are related to the molecular weight (amu).

Ref 1 and Ref 2 use Ethomeen T-12, which is ethoxylated tolowalkylamine from Akzo Nobel with the same nitrogen content.

The friction modifiers (FM) reported in Table 1 were prepared in a two step process. In the first step, the fatty acid was reacted with the polyamine and in the second step, the first step product (s) were post-treated with alkyl succinic anhydride. More particularly the first stage product (OL / TETA or ISA / TETA) was post-treated with alkyl succinic anhydride. Reaction stoichiometry is shown in Table 1. Various alkyl succinic anhydrides are also shown in Table 1. Example 1 described suitable reaction conditions for the first step. FM9 was prepared by applying the methods and conditions described in Example 1 for the first step and Example 2 for the second step. FM12 was prepared by applying the methods and conditions described in Example 1 for the first step and Example 3 for the second step. Other FMs in Table 1 were prepared using the same protocol in Example 1 and Example 2.

FM1 to Ref 1 provided 970 ppm nitrogen to the finished fluid. For this oil, the stability duration against oxidation was tested at 170 ° C. for 198 while bubbling air at a rate of 10 L / h.

The duration of stability for oxidation of oils containing FM11 to Ref 2 was only tested for 120 hours and the nitrogen contribution of the friction modifier was different at 375 ppm.

For example, when avoiding shedding problems and exhibiting sufficient resistance to oxidation, the friction modifier composition (such as FM-1 to FM-16) μ _s / μ _d values may generally be about 1.0 or less, and as further examples , Could be less than about 0.9.

The coefficient of kinetic friction, μ _d , is known for efficient torque transfer and therefore for fuel efficiency. High values were suitable for the parameter (μ _d ). For frictional durability, changes in the parameters resulting from aging of the oil will be minimized. High delta values meant that the oil lost its initial frictional properties as a result of thermal and oxidative stress.

In numerous places throughout the specification, references are made up of numerous US patents, European patent applications (published), PCT international patent publications, and references. All cited documents are fully incorporated into the above specification as if fully stated herein.

As used throughout the specification and claims, “a” and / or “an” may refer to one or more. Unless otherwise indicated, all numbers expressing quantities, properties such as molecular weight, percentages, ratios, reaction conditions, etc., as used in the specification and claims are, in all cases, modified by the term "about". It should be understood that Thus, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, each numerical parameter should be understood in terms of numbers not by attempting to limit the application of the doctrine of equivalents to the scope of the claims, but at least in terms of the reported significant Arabic numerals and the application of conventional rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value originally includes an error that essentially arises from the standard deviation found in its respective test measurement instrument.

While the present invention is described above in principle as a power transmission fluid of a transmission, the advantages of the fluid implementation are that the present invention provides gear oils, hydraulic fluids, heavy hydrodynamic fluids, industrial oils, power steering fluids, pump oils, tractors. Fluids and universal tractor fluids and device implementations intended to be similarly applied to other power transmission fluids incorporated in the fluids in accordance with the present invention and included in the range including gears, hydraulic mechanical devices, power, pumps and the like. do.

Other implementations of the invention will appear to those skilled in the art from consideration of the specification, drawings and implementations. It is intended that the spirit, specification and examples of the scope of the invention as indicated by the following claims be considered as exemplary only.

 Fluids described herein that relate to fluids having improved friction durability and μ / v properties on paper, metals, and enhanced friction materials can exhibit improved handling properties and improved anti-shudder durability.

Claims (36)

Fluid compositions comprising: (1) a large amount of base oil, and (2) an additive comprising: present in an amount of from 0.01% to 10% by weight relative to the fluid composition: (i) the reaction product of aliphatic carboxylic acid and polyamine, obtained under conditions sufficient to produce a mixture containing one or more compounds represented by formulas I and / or II, wherein the molar ratio of said carboxylic acid to polyamine is 1: Reaction products that are 1 to 2: 1;      (ii) (a) molar ratio 1: 1 of aliphatic carboxylic acid and polyamine under conditions sufficient to prepare a mixture of 1,2-disubstituted imidazolines comprising one or more compounds represented by Formulas I and / or II. To 2: 1, and then (b) the reaction product obtained by treatment under conditions for the preparation of further mixtures containing one or more compounds represented by Formulas III, IV, V and / or VI; or      (iii) at least one compound represented by formulas (I) and / or (II), and at least one compound represented by formulas (III) to (VI), produced by reacting an aliphatic carboxylic acid and a polyamine in a molar ratio of 1: 1 to 2: 1 Mixtures, wherein the formulas mentioned are as follows: [Formula I]

[Formula II]

[Formula III]

[Formula IV]

[Formula V]

And [Formula VI]

Wherein R ₁ and R ₂ are independent of one another and represent C ₃ to C ₃₀ linear or branched alkyl, alkenyl or aryl or heteroatom derivatives thereof, for example alkyl having a hetero atom as an example; R ₃ and R ₄ are independent of each other and are highly H, -OH, -OR, -COOH, -SH, -SR, straight chain, branched alkyl, alkenyl radicals and propylene, isobutylene and terminal, internal and vinylidene double bonds Selected from the group consisting of oligomeric or polymerizable hydrocarbyl groups derived from olefins, R represents an alkyl or alkenyl group having up to 30 carbon atoms, linear, branched or cyclic, n is a value from 0 to 5 to be). The method of claim 1, wherein the base oil is one or more natural oils, mixtures of natural oils, synthetic oils, mixtures of synthetic oils, mixtures of natural and synthetic oils, and Fischer-Tropsch or gas liquefaction. A fluid composition comprising a base oil derived by a to-liquid process. The fluid composition of claim 1, wherein the base oil has a kinematic viscosity of 2 centistokes to 10 centistokes at 100 ° C. The fluid composition of claim 1, wherein the fluid composition contains ashless dispersant. 5. The method of claim 1 or 4, wherein the fluid composition comprises one or more cleaning agents, another friction modifier, an antioxidant, an antiwear agent, an antifoaming agent, a viscosity index improver, a copper corrosion inhibitor, an anti-rust additive, a suture expanding agent, and And / or a fluid composition containing a metal deactivator. A transmission containing the fluid composition according to claim 1. 7. The transmission of claim 6, wherein the transmission comprises one selected from the group consisting of a continuously variable transmission, a dual clutch transmission, an automatic transmission, and a manual transmission. The fluid composition of claim 1 wherein the fluid is applied for use in a transmission that uses one or more electrically controlled converter clutches, sleeping torque converters, lock-up torque converters, start clutches, and one or more shifting clutches. The method of claim 1, wherein the fluid is used as a belt, chain, or disc continuous continuously variable transmission, a four-, five-, six-, or seven-speed automatic transmission, a manual transmission, an automated manual transmission, or a dual clutch transmission. Fluid composition applied for. The fluid composition of claim 1 wherein the fluid is applied for use as an industrial gear or an automobile gear. A vehicle comprising an engine and a transmission, wherein the transmission comprises the fluid according to claim 1. A vehicle comprising a differential device, the vehicle comprising a lubricant containing the fluid composition according to claim 1. A method of making a friction modifier compound comprising: (a) at a temperature ranging from 120 ° C. to 180 ° C. for 5 to 20 hours, at least one carboxylic acid R ₁ COOH with the formula H ₂ N— (CH ₂ CH ₂ NH) _x —CH ₂ , wherein x Reacts a linear polyamine represented by an integer from 1 to 10 in a molar ratio of 1: 1 to 2: 1, wherein the compound is represented by the following formulas I and II: [Formula I]

[Formula II]

Wherein R ₁ represents C ₃ to C ₃₀ linear or branched alkyl, alkenyl or aryl or heteroatom derivatives thereof; n is a value of 0 to 5). The process for producing a friction modifier compound according to claim 13, wherein R ₁ is represented by —C ₁₇ H ₃₅ . delete The method of claim 13, wherein the molar ratio is from 1.2: 1 to 1.6: 1. 17. The method of claim 16, wherein the molar ratio of carboxylic acid to polyamine is 4: 3. The method of claim 13, wherein the method produces a reaction product in which the ratio of at least one compound represented by Formula I to at least one compound represented by Formula II is 2: 1. The process according to claim 13, wherein the process converts the reaction product from step (a) into a compound (s) represented by the following formula (III) and at least one of the reactive nitrogen atoms in the compound of formula (I) or (II) A process for preparing a friction modifier compound, further comprising post-treatment with one or more carboxylic acid R ₂ COOH in an amount at which the indicated compound (s) can be obtained: [Formula III]

And [Formula IV]

Wherein R ₁ and R ₂ are independent of each other and represent a C ₃ to C ₃₀ linear or branched alkyl, alkenyl or aryl group or heteroatom derivative thereof. 14. The process of claim 13, wherein the process comprises reacting a reaction product comprising at least one compound represented by formula (I) and at least one compound represented by formula (II), wherein at least one portion of nitrogen in the compound is acrylated and represented by formulas (V) and (VI) A process for preparing a friction modifier compound, further comprising post-treatment with one or more organic acids or anhydrides thereof in an amount obtainable: [Formula V]

And [Formula VI]

Wherein R ₁ and R ₂ may be independent of each other and may represent a C ₃ to C ₃₀ linear or branched alkyl, alkenyl or aryl group, or a heteroatom derivative thereof; R ₃ and R ₄ may be independent of each other And from high olefins having H, -OH, -OR, -COOH, -SH, -SR, straight chain, beta branched alkyl, alkenyl radicals and propylene, isobutylene and terminal, internal and vinylidene double bonds May be selected from the group consisting of hydrocarbyl groups in the derived oligomer or polymerizable form, wherein R is an organic group having up to 30 carbon atoms and n is 0 to 5 value) A method of providing improved durability friction characteristics in a lubricated power train, the method comprising: 1) adding a fluid comprising (a) a base oil, and (b) a friction modifier to a power transmission device: (i) a reaction product having a molar ratio of aliphatic carboxylic acid and polyamine of 1: 1 to 2: 1, wherein the reaction product is obtained under conditions sufficient to prepare a mixture of 1,2-disubstituted imidazolines, The mixture is a reaction product containing one or more compounds represented by formulas I and / or II, (ii) reacting (a) the aliphatic carboxylic acid and the polyamine in a molar ratio of 1: 1 to 2: 1, wherein the reaction product is under sufficient conditions to prepare a mixture of 1,2-disubstituted imidazolines Obtained, the mixture containing one or more compounds represented by formulas I and / or II, and then (b) treated under conditions to provide one or more compounds represented by formulas III, IV, V, and / or VI. Reaction products obtained by the step of; or (iii) at least one compound represented by formula (I) or (II), and at least one compound represented by formula (III), (IV), (V) or (VI), produced by reacting an aliphatic carboxylic acid and a polyamine in a molar ratio of 1: 1 to 2: 1. Mixtures containing compounds: [Formula I]

[Formula II]

[Formula III]

[Formula IV]

[Formula V]

And [Formula VI]

Wherein R ₁ and R ₂ are independent of each other and represent a C ₃ to C ₃₀ linear or branched alkyl, alkenyl or aryl group, or a heteroatom derivative thereof; R ₃ and R ₄ are independent of each other, H, Oligomers derived from -OH, -OR, -COOH, -SH, -SR, straight chain, beta branched alkyl, alkenyl radicals and propylene, isobutylene and highly olefins with terminal, internal and vinylidene double bonds or Selected from the group consisting of hydrocarbyl groups in a polymerizable form, R represents an organic group having up to 30 carbon atoms, and n is 0 to 5 value); And 2) operating the fluid in the power transmission device, wherein the period of stability to oxidation of the fluid as power transmission fluid is improved compared to the performance of the fluidless transmission. 22. The method of claim 21, wherein the base oil has a kinematic viscosity of 2 centistokes to 10 centistokes at 100 ° C. The method of claim 21 wherein the fluid further contains ashless dispersant. 24. The method of claim 21 or 23, wherein the fluid is an antioxidant, antifoam, antiwear, anti-rust additive, detergent, viscosity index enhancer, copper corrosion inhibitor, suture expander, metal deactivator, and formulas I-VI. And at least one selected from the group consisting of friction modifiers other than those shown. 22. The method of claim 21 wherein the powertrain includes a transmission. 22. The method of claim 21 wherein the power transmission device comprises an industrial gear or an automobile gear. An additive composition comprising: (I) a reaction product of aliphatic carboxylic acids and polyamines obtained under conditions sufficient to produce a mixture containing one or more compounds represented by formulas (I) and / or (II), moles of said carboxylic acids to polyamines Reaction products having a ratio of 1: 1 to 2: 1;     (ii) (a) molar ratio 1: 1 of aliphatic carboxylic acid and polyamine under conditions sufficient to prepare a mixture of 1,2-disubstituted imidazolines comprising one or more compounds represented by Formulas I and / or II. To 2: 1, and then (b) the reaction product obtained by treatment under conditions for the preparation of further mixtures containing one or more compounds represented by Formulas III, IV, V and / or VI; or      (iii) at least one compound represented by formulas (I) and / or (II), and at least one compound represented by formulas (III) to (VI), produced by reacting an aliphatic carboxylic acid and a polyamine in a molar ratio of 1: 1 to 2: 1 Mixtures, wherein the formulas mentioned are as follows:     [Formula I]

[Formula II]

[Formula III]

[Formula IV]

[Formula V]

And [Formula VI]

Wherein R ₁ and R ₂ are independent of each other and represent a C ₃ to C ₃₀ linear or branched alkyl, alkenyl or aryl group, or a heteroatom derivative thereof; R ₃ and R ₄ are independent of each other, H, Oligomers derived from -OH, -OR, -COOH, -SH, -SR, straight chain, beta branched alkyl, alkenyl radicals and propylene, isobutylene and highly olefins with terminal, internal and vinylidene double bonds or Selected from the group consisting of hydrocarbyl groups in a polymerizable form, R represents an organic group having up to 30 carbon atoms, and n is 0 to 5 value) A method of improving the handling properties of a power transmission fluid, comprising the addition of an additive according to claim 27. Fluid compositions comprising: (1) a large amount of base oil, and (2) small amounts of additives comprising: (i) a mixture containing at least one compound represented by formula (I) and / or (II) produced by reacting an aliphatic carboxylic acid and a polyamine in a molar ratio of 1: 1 to 2: 1; or            (ii) at least one compound represented by formulas (I) and / or (II) and at least one compound represented by formulas (III) to (VI) produced by reacting an aliphatic carboxylic acid and a polyamine in a molar ratio of 1: 1 to 2: 1; Mixtures, where the formulas mentioned are as follows: [Formula I]

[Formula II]

[Formula III]

[Formula IV]

[Formula V]

And [Formula VI]

Wherein R ₁ and R ₂ are independent of one another and represent C ₃ to C ₃₀ linear or branched alkyl, alkenyl or aryl or heteroatom derivatives thereof, for example alkyl having a hetero atom as an example; R ₃ and R ₄ are independent of each other and are highly H, -OH, -OR, -COOH, -SH, -SR, straight chain, branched alkyl, alkenyl radicals and propylene, isobutylene and terminal, internal and vinylidene double bonds Selected from the group consisting of oligomeric or polymerizable hydrocarbyl groups derived from olefins, R represents an alkyl or alkenyl group having up to 30 carbon atoms, linear, branched or cyclic, n is a value from 0 to 5 to be). An additive composition comprising: (1) a mixture containing at least one compound represented by formula (I) and / or (II) produced by reacting an aliphatic carboxylic acid and a polyamine in a molar ratio of 1: 1 to 2: 1; or          (2) at least one compound represented by formulas (I) and / or (II) and at least one compound represented by formulas (III) to (VI) produced by reacting an aliphatic carboxylic acid and a polyamine in a molar ratio of 1: 1 to 2: 1; Mixtures, where the formulas mentioned are as follows: [Formula I]

[Formula II]

[Formula III]

[Formula IV]

[Formula V]

And [Formula VI]

Wherein R ₁ and R ₂ are independent of each other and represent a C ₃ to C ₃₀ linear or branched alkyl, alkenyl or aryl group, or a heteroatom derivative thereof; R ₃ and R ₄ are independent of each other, H, Oligomers derived from -OH, -OR, -COOH, -SH, -SR, straight chain, beta branched alkyl, alkenyl radicals and propylene, isobutylene and highly olefins with terminal, internal and vinylidene double bonds or Selected from the group consisting of hydrocarbyl groups in a polymerizable form, R represents an organic group having up to 30 carbon atoms, and n is 0 to 5 value) delete delete delete The additive composition of claim 27 wherein the molar ratio of carboxylic acid to polyamine is 1.2 to 1.6. 28. The composition of claim 27 wherein the carboxylic acid is one or more of lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, dodecenoic acid, hexadecenoic acid, oleic acid, iso-oleic acid, linoleic acid, arachid fatty acids, or Combination of; An additive composition comprising one or more selected from the group consisting of 4-dodecylbenzoic acid, 2-hexadecylnicotinic acid, and 4-polyisobutyl acid. 28. The polyamine of claim 27, wherein the polyamine comprises a polyethylene amine comprising an internal repeating unit of-(CH ₂ CH ₂ NH) _x -wherein x is an integer from 1 to 10; An additive composition comprising one or more selected from the group consisting of diethylene triamine, triethylene tetramine, and tetraethylene pentamine.

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