KR102425108B1 - Mixtures of friction modifiers to provide good friction performance to transmission fluids - Google Patents

Abstract

The mixture of friction modifiers provides excellent friction performance to a transmission fluid, the friction modifier comprising an N-substituted oxalic acid bisamide or amide-ester containing at least two hydrocarbyl groups of 12 to 22 carbon atoms; Amide or thioamide is one represented by R ¹ R ² NC(X)R ³ , wherein X is O or S, R ¹ and R ² are hydrocarbyl groups having at least 6 carbon atoms, and R ³ is a hydroxyalkyl group having 1 to 6 carbon atoms or a condensate thereof.

Description

MIXTURES OF FRICTION MODIFIERS TO PROVIDE GOOD FRICTION PERFORMANCE TO TRANSMISSION FLUIDS

The disclosed technology relates to fluids and additives for transmission, such as automatic transmission fluids.

In the automatic transmission market, where engineering changes are accelerated by the desire to reduce weight and increase transmission capability, automatic transmission fluids exhibiting a high coefficient of static friction are required to improve clutch holding force. For example, a continuously slipping torque converter clutch imposes precise friction requirements on the automatic transmission fluid (ATF). This fluid must have a good friction-to-slide velocity relationship, or an unpleasant phenomenon called shudder in the vehicle will occur. Transmission shudders are often referred to as "stick-slip" or "dynamic friction vibrations" and are a self-excited vibrational condition commonly encountered in sliding torque converter clutches. The frictional properties of this fluid and material system, along with the mechanical design and control of the transmission, determine the shudder sensitivity of the transmission. The plot of the measured coefficient of friction (μ) versus the sliding speed (V), often called the μ-V curve, has been found to correlate with the transmission shudder. Both theory and experimentation support that the positive to slightly negative slope region of this μ-V curve correlates with the good anti-shudder performance of transmission fluids. Fluids that allow the vehicle to operate without vibration or shudder are said to have good "anti-shudder" performance. This fluid should retain the above characteristics throughout its useful life. The lifetime of anti-shudder performance in a vehicle is commonly referred to as "anti-shudder durability". The Variable Speed Friction Tester (VSFT) measures the coefficient of friction for the speed, load, and sliding speed that simulates the friction material found in a transmission clutch, and correlates with the performance observed during actual use. These procedures are well documented in the literature; See, for example, publication #941883 of the Society of Automotive Engineers. It is also desirable to provide a lubricant with good friction performance to obtain a good torque capacity of an automatic transmission having a wet clutch.

The complex requirements of a high static coefficient of friction and a sustained positive slope are often incompatible with conventional ATF friction modifiers, which are very well documented in the patent literature. Many commonly used friction modifiers result in a low static friction coefficient, and are not sufficiently durable to be used in positive gradients.

U.S. Patent 8,691,740 (Vickerman et al., 2014.4.8.) discloses a friction modifier for an automatic transmission containing an N-substituted oxalic acid bisamide or amide-ester bearing at least two hydrocarbyl groups of 12 to 22 carbon atoms. Disclosed are compositions suitable for use as Other auxiliary friction modifiers may also be present. Other substances that may also be present include antiwear agents such as various long chain derivatives of hydroxy carboxylic acids such as tartrates, tartramids, tartrimides and citrates, among others.

U.S. Patent 8,148,306 (Bartley et al., 2012.4.3) discloses the product of hydroxy acids and amines as friction modifiers suitable for automatic transmission fluids. One example is an amide or thioamide represented by the formula R ¹ R ² NC(X)R ³ , wherein X is O or S, and R ¹ and R ² are each independently a hydrocarb having at least 6 carbon atoms. and R ³ is a hydroxyalkyl group having 1 to 6 carbon atoms or a group formed by condensation of this hydroxyalkyl group with an acylating agent through its hydroxy group).

U.S. Patent 8,450,255 (Sumiejski et al., May 28, 2013) discloses a friction modifier in which at least two hydrocarbyl groups are attached to a polar group or atom (eg, a nitrogen atom), the friction modifier comprising (a) at least the reaction product of at least one carboxylic acid or its equivalent with at least one aminoalcohol, (b) the reaction product of at least one carboxylic acid or its equivalent with at least one polyamine, (c) with the formula R ¹ R ² NC(X)R ³ amides or thioamides represented, wherein X is O or S, R ¹ and R ² are each independently a hydrocarbyl group having at least about 6 carbon atoms, and R ³ is 1 to about 6 carbon atoms is a hydroxyalkyl group or a group formed by the condensation of a hydroxyalkyl group with an acylating agent through its hydroxy group), (d) two hydrocarbyl groups with a polyhydroxyl-containing alkyl group or a polyhydroxyl-containing alkoxy group at least one tertiary amine containing an alkyl group, or (e) a mixture of two or more of (a), (b), (c) and (d) above.

The disclosed technology comprises (a) an oil of lubricating viscosity; (b) a hydro having from about 12 to about 22 carbon atoms (or from 12 to 20 or from 12 to 18 or from 12 to 16 or from 12 to 14 or from 14 to 20 or from 14 to 18 or from 14 to 16). 0.05 to 3.0 weight percent (or 0.1 to 2 or 0.3 to 1 or about 0.7%) of an N-substituted oxalic acid bisamide or amide-ester containing two or more carbyl groups; and (c) formula R ¹ R ² NC(X)R ³ , wherein X is O or S, and R ¹ and R ² are each independently at least 6 (or 8 to 24 or 10 to 18) an amide represented by a hydrocarbyl group having carbon atoms, and R ³ is a hydroxyalkyl group having 1 to 6 carbon atoms or a group formed by condensation of this hydroxyalkyl group with an acylating agent through its hydroxy group) or 0.05 to 3.0 weight percent (or 0.1 to 2% or 0.3 to 1 or about 0.7%) of thioamide.

According to one embodiment, the composition further comprises (d) from 1 to 6% by weight (or from 2 to 5.5 or from 3 to 5%) of a dispersant component comprising at least one succinimide dispersant, wherein said dispersant component comprises from 0.05 to 1 It contains boron by weight (or 0.1 to 0.5 or 0.2 to 0.4%) and has a TBN (oil free) of 40 to 90 (or 45 to 70 or 50 to 68).

The automatic transmission fluid is ideally higher than the normally achieved value of about 0.092 without increasing static friction (described in more detail below) to a value greater than about 0.135, resulting in high quasi-static friction (hereinafter referred to as high quasi-static friction). described in more detail). In addition, these values should be stable over time, ie it is desirable that the decrease in the coefficient of friction from the value at 500 test cycles to 2500 or 10,000 times is minimal. Ideally, this good performance should continue over the transmission operating temperature range. Meeting these goals will help provide a fluid with good torque capacity, anti-shudder performance and durability properties. The material of the present invention will be suitable for meeting one or more of these purposes.

Various features and aspects will be described below by way of non-limiting example.

One component used in certain aspects of the disclosed technology is an oil of lubricating viscosity. These oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation and hydrofinishing, crude oils, refined oils and re-refined oils and mixtures thereof.

Crude oils are oils obtained directly from natural or synthetic sources, generally with (or little) further refining treatment.

Refined oils are similar to crude oils except that they have been further treated in one or more refining steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like.

Rerefined oils, also known as reclaimed or reprocessed oils, are obtained by processes similar to those used to obtain refined oils, and are often further processed by techniques directed to the removal of spent additives and oil degradation products. processed

Natural oils useful for preparing the lubricants of the present invention include animal oils, vegetable oils (eg castor oil), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acidic paraffinic, naphthenic or mixed paraffinic-naphthenic types. - including treated mineral lubricating oils and oils derived from coal or shale or mixtures thereof.

Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerized and interpolymerized olefins (eg, polybutylene, polypropylene, propylene-isobutylene copolymer); poly(1-hexene), poly(1-octene), poly(1-decene), and mixtures thereof; alkyl-benzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (eg, biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologues or mixtures thereof.

Other synthetic lubricating oils include polyol esters (eg Priolube® 3970), diesters, liquid esters of phosphorus-containing acids (eg diethyl esters of tricresyl phosphate, trioctyl phosphate and decane phosphonic acid), or polymeric tetrahydrofuran. Synthetic oils may be produced by Fischer-Tropsch reactions and may generally be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. According to one embodiment, the oil may be prepared by a Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Compatibility Guidelines. The five base oil groups are: Group I (sulphur content >0.03 wt% and/or <90 wt% saturates, viscosity index 80-120); Group II (sulfur content ≤0.03 wt% and ≥90 wt% saturates, viscosity index 80-120); Group III (sulphur content ≤0.03 wt% and ≥90 wt% saturates, viscosity index ≥120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III or IV). In addition, the oil of lubricating viscosity may be an API Group II+ base oil, the term meaning a Group II base oil having a viscosity index of not less than 110 and less than 120, as described in SAE publications ["Design Practice: Passenger Car Automatic Transmissions", fourth Edition, AE-29, 2012, page 12-9] as well as US 8,216,448 col. 1, line 57.

The oil of lubricating viscosity may be an API group IV oil, or a mixture thereof, i.e. a polyalphaolefin. Polyalphaolefins can be prepared by metallocene catalyzed processes or from non-metallocene processes.

Oils of lubricating viscosity contain API Group I, Group II, Group III, Group IV, Group V oils or mixtures thereof.

Often the oils of lubricating viscosity are API Group I, Group II, Group II+, Group III, Group IV oils or mixtures thereof. Alternatively, oils of lubricating viscosity are often API Group II, Group II+, Group III or Group IV oils or mixtures thereof. Alternatively, oils of lubricating viscosity are often API Group II, Group II+, Group III oils or mixtures thereof.

The amount of oil of lubricating viscosity is generally the remaining amount after subtracting the sum of the amount of the above-mentioned additive and the amount of other performance additives from 100 wt%.

Lubricating compositions may be in the form of concentrates and/or fully formulated lubricants. If the lubricating composition of the present invention is in the form of a concentrate (which may be combined in whole or in part with additional oils to form the final lubricant), the ratio of the components of the present invention to the oil of lubricating viscosity and/or diluent oil is 1:99 to 99:1 (by weight), or 80:20 to 10:90 (by weight).

The present technology provides, as one component, N-substituted oxalic acid bisamides or amide-esters containing at least two hydrocarbyl groups having 12 to 22 carbon atoms. In certain embodiments, this compound does not contain a primary amine group (this group may not be present in any embodiments, whatever its specific chemical nature, and with or without other components). This material is useful as a friction modifier, especially for lubricating automatic transmissions. This component as a bisamide can be represented by the formula:

Two or more R groups in this structure are independently a group containing a hydrocarbyl group having 1 to 22 carbon atoms, and up to two R groups are hydrogen or a hydrocarbyl group of up to 10 carbon atoms. In other embodiments, one or more R groups independently contain 12 to 20, 12 to 18 or 12 to 16, 12 to 14, 14 to 20, 14 to 18 or 14 to 16 carbon atoms. can do. If there are two hydrocarbyl groups of 12 to 22 carbon atoms, both may be on the same nitrogen or on different nitrogen atoms; ie R ³ and R ⁴ or alternatively R ¹ and R ⁴ may be hydrogen. The hydrocarbyl groups may be the same or different within a given molecule in the overall composition or within a mixture of molecules.

Since at least two of the R ¹ , R ² , R ³ and R ⁴ groups contain a hydrocarbyl group of 12 to 22 carbon atoms, these groups may be hydrocarbyl groups such as, for example, an alkyl group of 12 to 22 carbon atoms. have. Alternatively, these groups may contain hydrocarbyl groups as part of a larger structure. That is, these groups may have a general structure such as R ⁵ R ⁶ NR ⁹ —, wherein one or both of R ⁵ and R ⁶ is a hydrocarbyl group having 12 to 22 carbons, optionally One of R ⁵ and R ⁶ may be hydrogen or a shorter hydrocarbyl group. R ⁹ will be a hydrocarbylene linking group such as methylene, ethylene, propylene or butylene, and in some cases a 1,3-propylene group. In certain embodiments, an alkyl group of 12 to 22 carbon atoms may contain both linear and cyclic species, such as up to 20% cyclic species.

According to some embodiments, the substituted oxalic acid bisamide may contain a material of approximately structure in which two of R ¹ , R ² , R ³ and R ⁴ are independently alkyl groups of 12 to 22 carbon atoms. These materials may have the following structures:

wherein each R ¹ and R ² is independently an alkyl group of, for example, 12 to 18 carbon atoms. These substances are obtained or can be obtained through known methods such as a process of reacting an alkyl oxamate such as ethyl oxamate with a dialkylamine.

In another embodiment, the N-substituted oxalic acid bisamide or amide-ester contains an amide-ester represented by the formula:

In this aspect, each R ¹ and R ² can independently be a hydrocarbyl group of 12 to 22 carbon atoms as defined elsewhere herein, and R ¹⁰ is a hydrocarbyl group of 1 to 22 carbon atoms. it can be a gimmick In certain embodiments, R ¹⁰ is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or t-butyl.

Long chain monoalkyl amines and dialkyl amines are commercially available. The hydrocarbyl group or groups of an amine can be expressed as a long-chain hydrocarbyl group, thus generally meaning a hydrocarbyl group containing from 12 to 22 carbon atoms. In the case of monoalkyl amines, i.e. primary amines, hydrocarbyl groups may contain mixtures of individual groups on different molecules having varying carbon numbers, generally falling within the range of 12 to 22 carbon atoms, although hydrocarbyl groups outside this range Molecules with bil groups may also exist. If a mixture of hydrocarbyl groups is present, the number of carbons may be predominantly an even number of carbons (eg, 12, 14, 16, 18, 20 or 22), as is characteristic of groups derived from many naturally occurring materials; or a mixed even and odd carbon number, or alternatively an odd number of carbons or a mixed odd number. These groups may be branched, linear or cyclic, saturated or unsaturated, or mixtures thereof. According to certain embodiments, a hydrocarbyl group may contain 16 to 18 carbon atoms, sometimes containing predominantly 16 or predominantly 18 carbon atoms. Specific examples include mixed "coco" groups, i.e. cocoalkyl groups, derived from cocoamines (mainly C12 and C14 amines), and mixed "tallow" groups, i.e. lowalkyl groups, and isostearyl groups. The tallow group may optionally be hydrogenated. Likewise, dialkyl amines, i.e. secondary amines, are available and may have one long-chain alkyl group and one short-chain alkyl group of 1 to 10 carbon atoms as described above, or may have two long-chain alkyl groups. can Examples of the latter include dicocoamine (available as Armeen 2C™) and ditallowamine. Others, such as isostearyl-coco amine, can generally be synthesized as described in Preparation B below.

In addition, two or more of the R ¹ , R ² , R ³ and R ⁴ groups may independently be N-hydrocarbyl-substituted or disubstituted aminoalkyl groups, wherein the hydrocarbyl substituent or substituents are 12 to 22 It is contemplated that those containing carbon atoms and alkyl moieties containing 1 to 4 carbon atoms. The chemical formula representing its general structure can be represented as follows:

wherein R ⁵ and R ⁷ are independently hydrocarbyl groups of from about 12 to about 22 carbon atoms, and R ⁶ and R ⁸ is independently hydrogen or a hydrocarbyl group of 1 to 22 carbon atoms, such as a hydrocarbyl group of up to 10 carbon atoms or a hydrocarbyl group of about 12 to about 22 carbon atoms. Suitable diamines for preparing such products include, for example, the "Duomeen" series of diamines available from Akzo, represented by the formula:

These polyamines are prepared by addition _of monoamine R ³ R ⁴ NH to acrylonitrile to produce an alkyl nitrile amine represented by the formula It can be prepared by providing:

In a related embodiment, the N-substituted oxalic acid bisamide or amide-ester may contain an amide-ester represented by the formula:

wherein R ⁵ and R ⁶ are independently a hydrocarbyl group having 12 to 22 carbon atoms as described above, and R ¹⁰ is a hydrocarbyl group having 1 to 22 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or t-butyl.

Examples of some specific materials for this component of the disclosure include those represented by the formula:

Here, coco and tallow are as defined above, and isostearyl represents the carbon structure of isostearic acid.

The bisamides disclosed herein can be prepared by known techniques, such as by reacting oxalic acid or a reactive equivalent thereof, such as ethyl oxamide or dimethyl oxalate with a suitable amine, as exemplified in the preparations of US Pat. No. 8,691,740. Amide-esters can be prepared by reacting a dialkyl oxalate with a suitable amine using a controlled amount of the amine (about 1:1 molar ratio), or a half ester-half-chloride (e.g. , ethyl 2-chloro-2-oxo-acetate) and an amine. Small amounts of amide-esters can be prepared according to the preparation of bisamides, and the relative amounts can be adjusted by known techniques.

The amount of oxalic acid bisamide or amide ester in the fully formulated lubricant can be from 0.05 to 3 weight percent, or from 0.1 to 2, 0.3 to 1 or about 0.7 weight percent.

Another component of the disclosed technology, component (c), is an amide or thioamide (at least one amide or thioamide) represented by the formula R ¹ R ² NC(X)R ³ , wherein X is O or S, and R ¹ and R ² are each independently a hydrocarbyl group having at least about 6 (or 8 to 24 or 10 to 18) carbon atoms, and R ³ is a hydroxyalkyl group of 1 to about 6 carbon atoms or a group formed by condensation of this hydroxyalkyl group with an acylating agent through its hydroxy group. This component can be considered the condensation product of a hydroxy acid or a thioic acid (described below) with a secondary amine, which can also be used as a friction modifier. The amine will contain a substituent hydrocarbyl group such as an alkyl group. This amine may be represented by the formula R ¹ R ² NH, wherein R ¹ and R ² are each independently at least 6 carbon atoms (eg, 6 to 30 carbon atoms or 8 to 24 carbon atoms, or 10 to 20 or 10 to 18 or 12 to 16). The R ¹ and R ² groups may be linear or branched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic and aromatic. In certain embodiments, these groups are alkyl groups, particularly linear alkyl groups. The R ¹ and R ² groups may be the same or different. A commercial example of a suitable amine is that sold under the trade name Armeen 2C™, which is believed to have two C ₁₂ alkyl groups. In one embodiment, the amine comprises a di-cocoalkyl amine or a cognate amine. Di-cocoalkyl amines (or di-cocoamines) are secondary amines in which the two R groups are predominantly C ₁₂ groups derived from coconut oil (although amounts of C ₈ to C ₁₈ are usually present). In certain embodiments, one or both of the R ¹ and R ² groups can be a 2-ethylhexyl group. In one embodiment, the amine moiety (or "substituted nitrogen moiety") R ¹ R ² N- of the amide or thioamide contains a (2-ethylhexyl)(hydrogenated tallow) amine moiety, wherein A “hydrogenated tallow” moiety is derived primarily from a tallow bearing a C ₁₈ group. It is understood that commercially available dialkylamines contain certain amounts of monoalkylamines and/or trialkylamines, and products made from these commercially available materials are to be considered to be included within the scope of the present invention. It can be seen that the trialkylamine component of

The amides or thioamides of the present invention may be considered as condensation products of the aforementioned amines with hydroxy acids or hydroxy thio acids or reactive equivalents thereof. When X is O, the amide is a derivative of a hydroxy acid which may be represented by the formula R ³ COOH. R ³ in the hydroxy acid (or hydroxy thioacid as the case may be) is a hydroxyalkyl group of 1 to 6 carbon atoms or such a hydroxyalkyl group is via its hydroxy group an acylating agent (which may also include a sulfur-containing acylating agent) It is a group formed by condensation with That is, the —OH group present in R ³ is itself potentially reactive and can condense with other acidic substances or reactive equivalents thereof, such as to form esters. That is, the hydroxy acid may condense with one or more additional molecules of the acid, such as, for example, glycolic acid. Examples of suitable hydroxy acids are glycolic acid, ie hydroxyacetic acid, HO—CH ₂ —COOH. Glycolic acid is readily available commercially in substantially pure form or as a 70% aqueous solution. When R ³ contains more than one carbon atom, the hydroxy group may be present on carbon 1 (α) or at another carbon in the chain (eg, β or ω). The carbon chain itself may be linear, branched or cyclic.

The amount of component (c) present in the composition of the present invention may be from 0.05 to 3.0% by weight of the final fluid formulation. Alternative amounts include 0.1 to 2%, 0.3 to 1%, or about 0.7% by weight. In the case of a concentrate, the amount will be proportionally higher.

Another component that may be present is a dispersant component, which may include a single dispersant species or a plurality of dispersant species. A dispersant may be expressed as "other than the compound described above", in which case some of the compounds described above may exhibit some dispersant properties. As an example, examples of "carboxy dispersants" are primarily described in US patents, such as 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,234405, 3,542,680, 3,576,165,235, 4,632, Re 26743, 3,632 .

(수평균분자량, M_n 으로 기재할 수도 있다)이 적어도 500인 것을 특징으로 할 수 있다. 일반적으로, 폴리알켄은

이 500 또는 700 또는 800 또는 900, 최대 5000, 또는 최대 2500, 또는 최대 2000 또는 최대 1500인 것을 특징으로 한다. 다른 양태에 따르면,

은 500 또는 700 또는 800부터 1200 또는 1300까지 다양하다. 한 양태에 따르면, 다분산도(

)는 적어도 1.5이다.A succinimide dispersant, a type of carboxyl dispersant, is prepared by reacting the aforementioned amine with a hydrocarbyl-substituted succinic anhydride (or a reactive equivalent thereof, such as an acid, acid halide or ester). Hydrocarbyl substituents generally have an average of at least 8, or 20, or 30 or 35 to up to 350, or up to 200, or up to 100 carbon atoms. In one embodiment, the hydrocarbyl group is derived from a polyalkene. These polyalkenes are

(It may be described as a number average molecular weight, M _n ) may be at least 500. In general, polyalkenes are

It is characterized as 500 or 700 or 800 or 900, at most 5000, or at most 2500, or at most 2000 or at most 1500. According to another aspect,

varies from 500 or 700 or 800 to 1200 or 1300. In one embodiment, the polydispersity (

) is at least 1.5.

Polyalkenes include homopolymers and interpolymers of polymerizable olefinic monomers having 2 to 16 or 2 to 6, or 2 to 4 carbon atoms. Olefins include monoolefins such as ethylene, propylene, 1-butene, isobutene and 1-octene; or a polyolefin-based monomer such as a diolefin-based monomer such as 1,3-butadiene and isoprene. In one embodiment, the polymer is a homopolymer. One example of a polymer is polybutene. In one example, about 50% of the polybutene is derived from isobutylene. Polyalkenes can be prepared according to conventional procedures.

In one embodiment, the succinic acylating agent reacts the polyalkene with an excess of maleic anhydride to form a substituted succinic acylating agent having at least 1.3, such as 1.5 or 1.7 or 1.8, the number of succinic acid groups per each equivalent of a substituent. provided and manufactured. The maximum number of succinic groups per substituent will generally not exceed 4.5 or 2.5 or 2.1 or 2.0. The preparation and use of substituted succinic acylating agents wherein the substituents are derived from the above polyolefins are described in US Pat. No. 4,234,435. Succinic acylating agents can be prepared by the chlorine assisted route or by heating (“ene”) reaction. This synthetic route is described in more detail in US Pat. No. 7,615,521 (see columns 3-5).

Substituted succinic acylating agents can react with amines, including the aforementioned amines and heavy amine products known as amine still bottoms. The amount of amine reacted with the acylating agent is generally such that it provides a molar ratio of CO:N from 1:2 to 1:0.25, or from 1:2 to 1:0.75, or from 1:1.4 to 1:0.95. In other embodiments, the CO:N ratio can be from 1:0.2 to 1:0.3, at such a ratio or at any other ratio, the final dispersant can be further treated, such as with dimercaptothiadiazole. When the amine is a primary imine, complete condensation to the imide can occur. In addition, various amounts of the amide product, such as amic acid, may be present. If the reaction is rather with an alcohol, the final dispersant will be an ester dispersant. Mixtures of amide, ester and possibly imide functional groups may be present, provided that both amine and alcohol functionalities are present, either in separate molecules or in the same molecule (as in the condensed amines described above). This dispersant is a so-called ester-amide dispersant.

"Amine dispersants" are reaction products of relatively high molecular weight aliphatic or cycloaliphatic halides and amines, such as polyalkylene polyamines. Examples thereof are described in US Pat. Nos. 3,275,554, 3,438,757, 3,454,555 and 3,565,804.

"Mannich dispersants" are reaction products of aldehydes (particularly formaldehyde) and amines (particularly polyalkylene polyamines) with alkyl phenols in which the alkyl group contains at least 30 carbon atoms. Examples of these are materials described in the following US patents: 3,036,003, 3,236,770, 3,414,347, 3,448,047, 3,461,172, 3,539,633, 3,586,629, 3,591,598, 3,634,515, 3,725,480, 3,726,882 and 3,980,569.

Post-treated dispersants may also be part of the disclosed technology. These dispersants generally contain carboxyl dispersants, amine dispersants or Mannich dispersants with urea, thiourea, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, nitrile, epoxide, boron compound, such as boric acid ("boric acid"). dispersants"), phosphorus compounds, such as acids or anhydrides of phosphorus, or reagents such as 2,5-dimercaptothiadiazole (DMTD). In certain embodiments, one or more of the individual dispersants may be post-treated with boron or DMTD, or with both boron and DMTD. Examples of materials of this kind are described in the following US patents: 3,200,107, 3,282,955, 3,367,943, 3,513,093, 3,639,242, 3,649,659, 3,442,808, 3,455,832, 3,579,450, 3,600,372, 3,708,422.

In one embodiment, the dispersant component will be present in an amount of 1 to 6% by weight of the lubricant formulation, or alternatively in an amount of 2 to 5.5 or 3 to 5%. If more than one type is present, this amount represents the sum of each dispersant that may be present. In one embodiment, the dispersant component contains one or more succinimide dispersants. According to one embodiment, the succinimide dispersant or dispersants will be borated, i.e. contain boron or will react with a boron species or boron oxidizing agent, so that the dispersant component as a whole is from 0.05 to 1 wt % boron, or alternatively 0.1 to 0.7% or 0.2 to 0.6%. If multiple succinimide dispersants are present, the boron may be retained or bound to one or more dispersants, while one or more other dispersants will not be borated (the form of reaction or association of boron with the dispersant species is not restrictive). The TBN of the total dispersant component may be from 40 to 100, or from 40 to 95, or from 40 to 90, or from 45 to 70, or from 50 to 68 on an oil-free basis [TBN, or the total base is (total base number) is the amount of acid in milligrams of KOH per gram of sample required to titrate the sample to a specified endpoint, as defined in ASTM D-794].

In one embodiment, the dispersant component has a first borated succinate having a boron content of about 0.1 to about 1 weight percent, or 0.3 to 0.8, or 0.5 to 0.7 weight percent, and a TBN of 4 to 90 or 50 to 70 in certain embodiments. Contains an imide dispersant component (ie, one or more distinct species). In this aspect, the dispersant component may also contain a second dispersant component (one or more distinct species) that is not borated or less borated than the first dispersant component. Accordingly, the second succinimide dispersant component may have a boron content of less than 0.1% by weight, or less than 0.05 or 0.01% by weight, or may be boron-free. The TBN of the second succinimide dispersant component may be from 40 to 80, from 40 to 70 or from 50 to 60 according to certain embodiments.

In certain embodiments, the dispersant component contains more than one individual dispersant species, such as more than one individual succinimide dispersant species. One or more of these may be a succinimide dispersant that is reacted (or post-treated) with at least one of terephthalic acid, an inorganic phosphorus compound, or a dimercaptothiadiazole compound. For example, according to one embodiment there may be three separate succinimide dispersant species, wherein one may be treated with boron and terephthalic acid, the second may be treated with boron, terephthalic acid and dimercaptothiadiazole, and three The second may not be treated with any post-treatment agent. Many such combinations of individual dispersants will be apparent to those skilled in the art; Such combinations may be selected such that a particular amount of boron is met in the total dispersant component.

Other additives may be present in the lubricants of the disclosed technology. One commonly used component is a viscosity modifier, also called a viscosity improver. Viscosity modifiers (VM) and dispersants Viscosity modifiers (DVM) are well known. Examples of VMs and DVMs may include polymethacrylates, polyacrylates, polyolefins, styrene-maleic acid ester copolymers, and similar polymeric materials such as homopolymers, copolymers and graft copolymers. The DVM may contain nitrogen-containing methacrylate polymers, such as nitrogen-containing methacrylate polymers derived from methyl methacrylate and dimethyl aminopropylamine.

Examples of commercially available VMs, DVMs and their chemical classes may include: polyisobutylene (eg Indopol™ (BP Amoco) or Parapol™ (ExxonMobil); olefin copolymers (eg , Lubrizol™ 7060, 7065 and 7067 (Lubrizol) and Lucant™ HC-2000L and HC-600 (Mitsui); hydrogenated styrene-diene copolymers such as Shellvis™ 40 and 50 (Shell) and LZ® 7308 and 7318 (Lubrizol); styrene/maleate copolymers that are dispersant copolymers (e.g. LZ® 3702 and 3715, Lubrizol); polymethacrylates, some of which have dispersant properties (e.g. Viscoplex™ series (RohMax), Hitec) ™ series (Afton), LZ 7702™, LZ 7727™, LZ 7725™ and LZ 7720C™ (Lubrizol); olefin-grafted-polymethacrylate polymers such as Viscoplex™ 2-500 and 2-600 (RohMax) ), and hydrogenated polyisoprene star polymers (such as Shellvis™ 200 and 260, Shell), also include Lubrizol's Asteric™ polymers (methacrylate polymers with a radial or star structure). Viscosity modifiers are described in U.S. Pat. can

Another component that may be used in the compositions used in the present technology is an auxiliary friction modifier. These friction modifiers are well known to those skilled in the art. A list of friction modifiers that can be used is included in US Pat. Nos. 4,792,410, 5,395,539, 5,484,543 and 6,660,695. U.S. Pat. No. 5,110,488 discloses metal salts of fatty acids, particularly zinc salts, useful as friction modifiers. A list of auxiliary friction modifiers that may be used may include:

Fatty phosphite borated alkoxylated fatty amine

Metal salts of fatty acids amides fatty acids

Fatty Epoxide Sulfurized Olefins

Borated Fat Epoxide Fat Imidazoline

In addition to the aforementioned fatty amines, carboxylic acids and polyalkylene-polyamines

Other fatty amine condensation products

Metal salts of glycerol esters alkyl salicylates

Amine salt of borated glycerol ester alkylphosphoric acid

Alkoxylated fatty amine ethoxylated alcohol

oxazoline imidazoline

hydroxyalkyl amides polyhydroxy tertiary amines

and mixtures of two or more thereof.

Representative examples of each friction modifier of this kind are known and commercially available. For example, the fatty phosphite may generally be of the formula (RO) ₂ PHO or (RO)(HO)PHO, where R may be an alkyl or alkenyl group of sufficient length to impart oil solubility. Suitable phosphites are commercially available and may be synthesized as described in US Pat. No. 4,752,416.

Borated fatty epoxides that may be used are disclosed in Canadian Patent 1,188,704. Such oil soluble boron-containing compositions may be prepared by reacting a boron source, such as boric acid or boron trioxide, with a fatty epoxide, which may contain at least 8 carbon atoms. Non-borated fatty epoxides would also be useful as auxiliary friction modifiers.

Borated amines that can be used are disclosed in US Pat. No. 4,622,158. Borated amine friction modifiers (eg, borated alkoxylated fatty amines) can be prepared by reacting the aforementioned boron compounds with corresponding amines, such as simple fatty amines and hydroxyl containing tertiary amines. Amines useful for preparing borated amines may include commercially available alkoxylated fatty amines known under the trade name “ETHOMEEN” and available from Akzo Nobel, such as bis[2-hydroxyethyl]-cocoamine , polyoxyethylene [10] cocoamine, bis [2-hydroxyethyl] - soiamine, bis [2-hydroxyethyl] - tallowamine, polyoxyethylene- [5] tallowamine, bis [2- hydroxyethyl]oleylamine, bis[2-hydroxyethyl]octadecylamine, and polyoxyethylene[15]-octadecylamine. Such amines are described in US Pat. No. 4,741,848.

Alkoxylated fatty amines and fatty amines themselves (eg, oleylamine) may be useful as friction modifiers. These amines are commercially available.

Both borated fatty acid esters of glycerol and unborated fatty acid esters of glycerol can be used as friction modifiers. Borated fatty acid esters of glycerol can be prepared by boronation of fatty acid esters of glycerol with a boron source such as boric acid. The fatty acid ester of glycerol itself can be prepared by a variety of methods known in the art. Many of these esters, such as glycerol monooleate and glycerol tallowate, are produced on a commercial scale. Commercial glycerol monooleate may contain a mixture of 45 to 55 weight percent monoester and 55 to 45 weight percent diester.

Fatty acids can be used to prepare the glycerol esters: fatty acids can also be used to prepare their metal salts, amides and imidazolines, all of which can also be used as friction modifiers. Fatty acids may contain from 6 to 24 carbon atoms, or from 8 to 18 carbon atoms. A useful acid may be oleic acid.

Amides of fatty acids may be those prepared by condensation with ammonia or with primary or secondary amines such as diethylamine and diethanolamine. Fatty imidazolines may include cyclic condensation products of diamines or polyamines, such as polyethylenepolyamines, with acids. In one embodiment, the friction modifier may be a condensation product of a polyalkylene polyamine with a C8 to C24 fatty acid, such as a product of tetraethylenepentamine and isostearic acid. The condensation product of a carboxylic acid with a polyalkyleneamine may be an imidazoline or an amide.

Fatty acids may also be present as their metal salts, such as zinc salts. This zinc salt can be acidic, neutral or basic (overbased). This salt can be prepared by reacting a zinc-containing reagent with a carboxylic acid or a salt thereof. A useful method for preparing such salts is to react carboxylic acids with zinc oxide. Useful carboxylic acids are those described above. Suitable carboxylic acids include those represented by the formula RCOOH, wherein R is an aliphatic or cycloaliphatic hydrocarbon radical. Among these are those wherein R is a fatty group such as stearyl, oleyl, linoleyl or palmityl. Also suitable are zinc salts in which the zinc is present in a stoichiometric excess than is necessary to prepare the neutral salt. Salts in which zinc is present in 1.1 to 1.8 times the stoichiometric amount, such as 1.3 to 1.6 times the stoichiometric amount of zinc, may be used. Such zinc carboxylates are known in the art and are described in US Pat. No. 3,367,869. Metal salts may also include calcium salts. Examples may include overbased calcium salts.

Sulfurized olefins are also known commercially available materials used as friction modifiers. Suitable sulfurized olefins are those prepared according to the detailed teachings of US Pat. Nos. 4,957,651 and 4,959,168. It may also be a cosulfurized mixture of two or more reactants selected from the group consisting of at least one fatty acid ester of a polyhydric alcohol, at least one fatty acid, at least one olefin and at least one fatty acid ester of a monohydric alcohol. have. The olefin component may be an aliphatic olefin, usually containing from 4 to 40 carbon atoms. Mixtures of these olefins are commercially available. Sulfidizing agents useful in the process of the present invention include elemental sulfur, hydrogen sulfide, sulfur halide plus sodium sulfide, and mixtures of hydrogen sulfide with sulfur or sulfur dioxide.

Metal salts of alkyl salicylates include calcium salts and other salts of long chain (eg, C12 to C16) alkyl-substituted salicylic acids.

Amine salts of alkylphosphoric acids include salts of oleyl and other long chain esters of phosphoric acid with amines such as tertiary-aliphatic primary amines, sold under the trade name Primene™.

The amount of auxiliary friction modifier, if present, may be 0.1 to 1.5% by weight of the lubricating composition, such as 0.2 to 1.0 or 0.25 to 0.75%. However, in some embodiments, the amount of auxiliary friction modifier is less than 0.2% by weight or less than 0.1% by weight, such as 0.01 to 0.1%.

Compositions of the present technology may also include detergents. As used herein, detergents are metal salts of organic acids. The organic acid moiety of the detergent may be a sulfonate, carboxylate, phenate or salicylate. The metal moiety of the detergent may be an alkali or alkaline earth metal. Suitable metals include sodium, calcium, potassium and magnesium. In general, detergents are overbased, meaning that there is a stoichiometric excess of the metal base than is needed to form the neutral metal salt.

Suitable overbased organic salts include sulfonate salts that are substantially lipophilic in nature and are prepared from organic materials. Organic sulfonates are well known substances in the lubricant and detergent art. The sulfonate compound will contain an average of 10 to 40 carbon atoms, such as 12 to 36 carbon atoms, or 14 to 32 carbon atoms. Likewise, phenates, salicylates and carboxylates are substantially lipophilic in nature.

Although the present invention allows for carbon atoms in aromatic or paraffinic form, alkylated aromatics are employed in certain embodiments. Although naphthalene-based materials can be used, the best aromatic is the benzene moiety.

Accordingly, suitable compositions include overbased monosulfonated alkylated benzenes, such as monoalkylated benzenes. In general, the alkyl benzene fraction is obtained from a still bottom source and is monoalkylated or dialkylated. It is believed in the present invention that monoalkylated aromatics have better overall properties than dialkylated aromatics.

It is sometimes preferred in the present invention to use mixtures of monoalkylated aromatics (benzenes) to obtain monoalkylated salts (benzene sulfonates). Mixtures in which a significant portion of the composition contains a polymer of propylene as a source of alkyl groups can aid in the solubility of the salt. The use of monofunctional (eg monosulfonated) materials avoids crosslinking of the molecules, resulting in less salt precipitation from the lubricant. It is also often desirable to use alkylated benzenes prepared by alkylation with α-olefins.

Salts may be "overbased". By overbased it is meant that a stoichiometric excess of the metal base is present above the amount required for the anion of the neutral salt. The excess metal from overbased has the effect of neutralizing acids that can build up in the lubricant. In general, the excess metal will be present in a ratio of up to 30:1 on an equivalent basis, such as 5:1 to 18:1, above the amount necessary to neutralize the anion. Overbased materials are often carbonized, i.e. react with carbon dioxide to help tolerate excess equivalents of metal.

The amount of overbased salt employed in the composition is generally from 0.025 to 3% by weight on an oil-free basis, such as from 0.1 to 1.0%. In other embodiments, the final lubricating composition may contain no, substantially no, or only minor amounts of detergent. That is, for example in the case of a calcium overbased detergent, the amount is such that it provides less than 250 ppm calcium, such as 0-250, 1-200 or 10-150 or 20-100 or 30-50 ppm calcium, or 0 It may be present in an amount less than any of the amounts described above. This is in contrast to more conventional formulations, which may contain sufficient calcium detergent to provide 300 to 600 ppm of calcium. Overbased salts generally have no more than about 50% oil and have a TBN in the range of 10-180 or 10-600 (on an oil-free basis). Borated and unborated overbased detergents are described in US Pat. Nos. 5,403,501 and 4,792,410.

The composition of the present invention may also comprise at least one acid of phosphorus, an acid salt of phosphorus, an acid ester of phosphorus or a derivative thereof, such as a sulfur-containing analog, in an amount of 0.002 to 1.0% by weight. Such acids, salts, esters or derivatives of phosphorus include phosphoric acid, phosphorous acid, acid esters of phosphorus or salts thereof, phosphites, phosphorus-containing amides, phosphorus-containing carboxylic acids or esters, phosphorus-containing ethers and mixtures thereof.

In one embodiment, the acid, ester or derivative of phosphorus can be an organic or inorganic acid of phosphorus, an acid ester of phosphorus, an acid salt of phosphorus, or a derivative thereof. Acids of phosphorus include phosphoric acid, phosphonic acid, phosphinic acid and thiophosphoric acid such as dithiophosphoric acid as well as monothiophosphoric acid, thiophosphinic acid and thiophosphonic acid. One group of phosphorus compounds is an alkylphosphoric acid monoalkyl primary amine salt represented by the formula:

wherein R ¹ , R ² , R ³ may be an alkyl or hydrocarbyl group, or one of R ¹ and R ² may be H. This material may be a 1:1 mixture of a dialkyl phosphoric acid ester and a monoalkyl phosphoric acid ester. Compounds of this class are described in US Pat. No. 5,354,484.

85% phosphoric acid is a suitable material for addition to a fully formulated composition and may be included at a level of 0.01 to 0.3% by weight based on the weight of the composition, such as 0.03 to 0.2 or 0.03 to 0.1%.

Other phosphorus-containing materials that may be present include dialkylphosphites (sometimes called dialkyl hydrogen phosphonates), such as dibutyl phosphite. Still other phosphorus materials include phosphorylated hydroxy-substituted triesters of phosphorothioic acids and their amine salts, as well as sulfur-free hydroxy-substituted diesters of phosphoric acid, sulfur-free phosphorylated hydroxy- substituted diesters or triesters, and amine salts thereof. These materials are described in more detail in US patent application US 2008-0182770.

Other materials may also be included in the composition of the present technology in some cases, provided that they are not incompatible with the above-mentioned necessary components or specifications. Such substances include antioxidants (i.e., antioxidants) such as hindered phenolic antioxidants, secondary aromatic amine antioxidants such as dinonyldiphenylamine, as well as mononos with other alkyl substituents such as monooctyl or dioctyl. Known variants such as nyldiphenylamine and diphenylamine, sulfurized phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, and organic sulfides, disulfides, and polysulfides such as 2-hydroxyalkyl, alkyl thioethers or 1-t-dodecylthio-2-propanol or sulfurized 4-carbobutoxycyclohexene or other sulfurized olefins. Corrosion inhibitors such as tolyl triazole and dimercaptothiadiazole and oil soluble derivatives of these substances may also be included. Other optional ingredients include seal swell compositions such as isodecyl sulfolane or phthalate esters formulated to maintain the flexibility of the seal. Pour point depressants may also be included, such as alkylnaphthalenes, polymethacrylates, vinyl acetate/fumarate or /maleate copolymers, and styrene/maleate copolymers. Other materials include antiwear agents, such as zinc dialkyldithiophosphate, tridecyl adipate, and various long chain derivatives of hydroxy carboxylic acids, such as tartrate, tartramid, tartrimide, and citrate as described in US Application 2006-0183647. to be. Such optional materials are known to those skilled in the art and are generally commercially available and are described in more detail in published European Patent Application 761,805. In addition, known substances such as corrosion inhibitors (eg, tolyltriazole, dimercaptothiadiazole), dyes, glidants, odor blockers, and defoamers may also be included. Organoborate esters and organoborates may also be included.

The ingredients may be present in the form of a fully formulated lubricant or in the form of a concentrate in a smaller amount of lubricating oil. If they are present as concentrates, their concentrations will generally be directly proportional to the concentrations present in dilute form in the final blend.

As used herein, the terms "hydrocarbyl substituent" or "hydrocarbyl group" are used in their ordinary meanings known to those skilled in the art. Specifically, it refers to a group in which a carbon atom is directly attached to the remainder of the molecule and has predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

- hydrocarbon substituents, i.e. aliphatic (e.g. alkyl or alkenyl), cycloaliphatic (e.g. cycloalkyl, cycloalkenyl) substituents and aromatic-, aliphatic- and cycloaliphatic-substituted aromatic substituents, as well as wherein the ring is different from the molecule cyclic substituents completed through a site (eg, two substituents taken together to form a ring);

- substituted hydrocarbon substituents, i.e. substituents containing non-hydrocarbon groups that do not alter the main hydrocarbon properties of the substituent in the context of the present invention (e.g. halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmer capto, nitro, nitroso and sulfoxy);

-heterosubstituents, i.e. substituents which, in the context of the present invention, have predominantly hydrocarbon character, but which contain atoms other than carbon in a ring or chain composed of carbon atoms and which include substituents such as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen and nitrogen. In general, heteroatoms will be present with no more than 2 or no more than 1 per 10 carbon atoms of the hydrocarbyl group; Generally there will be no heteroatoms in the hydrocarbyl group.

It is known that several of the substances described above interact in the final formulation so that the ingredients in the final formulation may differ from those initially added. For example, metal ions (eg, metal ions in detergents) can migrate to other acidic or anionic sites of other molecules. The products thus formed, such as those formed when the compositions of the present invention are used for their intended use, are not readily descriptive. Nevertheless, all such modifications and reaction products are included within the scope of this invention; The present invention encompasses compositions prepared by mixing the aforementioned ingredients.

The amount of the phosphorus-containing compound or compounds present in the composition of the present invention may, according to certain embodiments, be from 0.01 to 2% by weight, alternatively from 0.02 to 1% by weight or from 0.05 to 0.5% by weight. Correspondingly, the total phosphorus content of the composition may of course be, for example, 0.01 to 0.3% by weight, 0.003 or 0.03 to 0.20% by weight or 0.05 to 0.15% by weight, depending on the phosphorus content of the particular compound selected. According to certain embodiments, formulations of the disclosed technology may or may not contain phosphorus in the form of zinc dialkyldithiophosphates. In some embodiments, the zinc dialkyldithiophosphate is present in less than 0.1% or less than 0.01% by weight. Such materials can be represented by the formula:

wherein R ⁸ and R ⁹ are independently a hydrocarbyl group such as an alkyl, cycloalkyl, aralkyl or alkaryl group having 3 to 20 carbon atoms, or 3 to 16 or 3 to 12 carbon atoms. This material is generally prepared by reacting with phosphorus pentasulfide one or a mixture of alcohols R ⁸ OH and R ⁹ OH, which may be mixtures of secondary and primary alcohols, such as isopropanol and 4-methyl-2-pentanol. It is prepared by providing an acid and then neutralizing it with zinc oxide.

When the composition is in the form of a concentrate, the relative amounts of the various components will increase proportionally by a factor such as 10 or the like (except for oils of lubricating viscosity, which will decrease correspondingly)

As used herein, the term "condensation product" refers to esters, amides, imides, and reactive equivalents of acids or acids with alcohols or amines, whether or not the condensation reaction is carried out directly to the actual product (e.g., acid halides, anhydrides or esters), which may be prepared by the condensation reaction. Thus, for example, certain esters can be prepared by transesterification rather than direct condensation. The resulting product is still considered a condensation product.

The amounts of each chemical component stated are, unless otherwise stated, excluding any solvents or diluent oils that may ordinarily be present in commercially available materials, i.e., based on the active chemical. However, unless otherwise indicated, each chemical or composition referred to herein should be construed as being of a commercial grade, which may possess isomers, by-products, derivatives and other materials normally known to exist in commercial grades.

As used herein, the terms "hydrocarbyl substituent" or "hydrocarbyl group" are used in their ordinary meanings known to those skilled in the art. Specifically, the term refers to groups having carbon atoms directly attached to the remainder of the molecule and exhibiting predominantly hydrocarbon properties. Examples of hydrocarbyl groups include hydrocarbon substituents such as aliphatic, cycloaliphatic and aromatic substituents; substituted hydrocarbon substituents, ie those containing non-hydrocarbon groups which in the context of the present invention do not primarily alter the hydrocarbon nature of the substituent; and hetero substituents, i.e., substituents which likewise have predominantly hydrocarbon character, but which contain atoms other than carbon in the ring or chain. A more detailed description of the term "hydrocarbyl substituent" or "hydrocarbyl group" is found in paragraphs [0137] to [0141] of published application US 2010-0197536.

It is known that several of the substances described above interact in the final formulation, so that the ingredients of the final formulation may differ from the ingredients initially added. For example, metal ions (eg, metal ions in detergents) can migrate to other acidic or anionic sites of other molecules. The products thus formed, such as those formed when the compositions of the present invention are used for their intended use, are not readily descriptive. Nevertheless, all such modifications and reaction products are included within the scope of this invention; The present invention encompasses compositions prepared by mixing the aforementioned ingredients.

The present invention is useful for providing good friction performance to transmission fluids, which will be better understood with reference to the following examples.

Example

The following formulations were prepared for testing:

Starting lubricants representing typical or conventional lubricants for automatic transmissions were prepared containing the following components (each component other than oil is expressed on an oil-free basis, all percentages are by weight):

oil of lubricating viscosity (amount to make a total of 100%);

Polymethacrylate viscosity modifier, 3.4%

Pour point depressant, 0.2%

Antiwear agent: 0.28%, such as dibutyl phosphite and di(long chain alkyl) phosphite

Succinimide dispersant: 4.28%, such as borated succinimide dispersant(s) and dimercaptothiadiazole-treated dispersant(s)

Seal Inflator: 0.5%

Corrosion inhibitor: 0.06%

Antioxidants: 1.1%, including hindered phenolic ester antioxidants and aromatic amine antioxidants

Detergent: 0.18% overbased calcium sulfonate detergent (low TBN and high TBN material)

Typical friction modifier package: 0.61%, such as phosphoric acid (85%), borate ester, polyoxyethylene tallowalkylamine, hydroxyethyl heptadecenyl imidazoline, and long chain hydroxyalkylamine

Minor amounts of other conventional additives (including, for example, defoamers, dyes and fragrance additive(s)).

Example 1 further comprises 0.70% by weight of the condensation product (amide) of dicocoamine and glycolic acid in a starting lubricant formed by the reaction of dimethyloxalate with N,N-di(C18 alkyl)propylene-1,3-diamine 0.70% by weight of bisamides (the C18 alkyl group is characteristic of the isostearic acid structure).

Example 2 The same starting lubricant as Example 1 was used, except that the amount of long-chain hydroxyalkylamine was less than that of 0.01%, the antioxidant component contained an additional 0.4% of substituted hydrocarbyl sulfide, and other conventional additives. are slightly different in certain small quantities. The formulation of Example 2 is a bis formed by the reaction of dimethyl oxalate with N,N-di(C18alkyl)propylene-1,3-diamine (the C18 alkyl group is characteristic of the isostearic acid structure) in a modified starting lubricant. 0.70% by weight of amide.

For Reference Examples B (138), C (129) and D (123), similar starting lubricants are used, but the composition and amounts of any specific ingredients generally differ as follows:

Reference Example B (138) : Amount of anti-wear component: 0.28%

Amount of dispersant component: 3.71%

Amount of antioxidant component: 1.5%

Amount of cleaning agent component: 0.29%

Amount of conventional friction modifier component: 0.51%

Reference Example B (138) further contains 0.60% by weight of a bisamide formed by the reaction of dimethyl oxalate with N,N-di(C18 alkyl)propylene-1,3-diamine.

Reference Example C (129) : Amount of anti-wear component: 0.2%

Amount of dispersant component: 3.77%

Amount of corrosion inhibitor component: 0.11%

Amount of antioxidant component: 1.5%

Amount of cleaning agent component: 0.23%

Amount of conventional friction modifier component: 0.62%

Reference Example C (129) further contains 0.75% by weight of a condensation product (amide) of dicocoamine and glycolic acid.

Reference Example D (123) : Amount of anti-wear component: 0.2%

Amount of dispersant component: 3.99%

Amount of corrosion inhibitor component: 0.12%

Amount of antioxidant component: 1.5%

Amount of cleaning agent component: 0.10%

Amount of conventional friction modifier component: 0.57%

Reference Example D (123) further contains 0.66% by weight of a condensation product (amide) of dicocoamine and glycolic acid.

The formulations thus prepared were subjected to a friction test involving repeated engagement and disengagement of a paper-based friction disk and a lubricated steel clutch plate. This test was performed on a SAE No.2 Universal Wet Friction Material Test Machine, or an equivalent machine conforming to GK or DKA specifications. Measurements were recorded at 500, 2500 and 10,000 dissociation cycles.

All measurements were performed with the lubricant formulation maintained at 100°C. The first measurement is the "quasi-static" coefficient of friction. For this measurement, the clutch was released immediately after shifting to 10 rpm to reach the 270°C steel plate temperature under high temperature conditions. The quasi-static coefficient of friction was measured 0.5 s after separation was initiated and the sliding speed stabilized. The second measurement is the "static" coefficient of friction, which is defined as the coefficient of friction when the clutch plate moves at a relative speed of 10 rpm immediately after disengagement. Likewise, dynamic coefficients of friction were recorded at 90%, 50% and 10% slide speeds when the clutch is engaged.

The test results are presented in the table below. For each entry, the relevant coefficient of friction was recorded, namely at 500 cycles (early test), 2500 cycles (mid-test) and 10,000 cycles (end of test):

The results show that the inventive example containing both the oxalic acid bisamide and the amide of component (c) exhibits good friction performance in this test, remaining relatively stable for 500 to 10,000 cycles. The quasi-static coefficient of friction is a high and stable value of 1.02 to 1.09. The static friction coefficient is substantially a stable value that does not exceed 0.135.

Each of the aforementioned documents is incorporated herein by reference, including all prior applications for which priority is claimed, whether or not specifically listed above. The mention of any document is not an admission that this document is qualified as prior art or constitutes the general knowledge of one skilled in any jurisdiction. In the present specification, all numerical quantities specifying amounts of substances, reaction conditions, molecular weights, number of carbon atoms, etc., except in the examples or where otherwise expressly indicated, the word "about" may be modified as the case may be. It should be understood as doing It should be understood that the upper and lower amounts, ranges, and ratio limits set forth herein may be independently combined. Likewise, ranges and amounts for each component of the present invention may be used in conjunction with ranges or amounts for any other component.

As used herein, the transitional word "comprising" is synonymous with "comprising," "having," or "characterized by," is implicit or open, and does not exclude components or method steps not further mentioned. . However, whenever referenced to "comprising" herein, the term also encompasses the phrases "consisting essentially of" and "consisting of" as alternative aspects, wherein "consisting of" means that any component or step not specified is In exclusion, "consisting essentially of" is intended to permit the inclusion of additional, unrecited components or steps that do not materially affect the essential or basic and novel properties of the composition or method under consideration. The expression "consisting of" or "consisting essentially of, when applied to one component of a claim, is intended to limit all species of the kind expressed by that component, notwithstanding the presence of "comprising" elsewhere in the claim. .

While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the scope of the invention. In this regard, the scope of the present invention should be limited only by the following claims. In certain jurisdictions, recitation of narrower values of one or more of a numerical range or recitation of a narrower selection of ingredients from a broader list means that such recitations are indicative of preferred embodiments.

Claims (16)

(a) oils of lubricating viscosity;
(b) 0.05 to 3.0% by weight of an N-substituted oxalic acid bisamide or amide-ester containing at least two hydrocarbyl groups having 12 to 22 carbon atoms; and
(c) 0.05 to 3.0 wt% of an amide or thioamide represented by the formula R ¹ R ² NC(X)R ³
As a composition containing,
wherein X is O or S, R ¹ and R ² are each independently a hydrocarbyl group having at least 6 carbon atoms, R ³ is a hydroxyalkyl group having 1 to 6 carbon atoms or the hydroxyalkyl group A group formed by the condensation of the hydroxyalkyl group with an acylating agent through a hydroxyl group of
composition. The dispersant component according to claim 1, further comprising (d) 1 to 6% by weight of a dispersant component containing at least one succinimide dispersant, said dispersant component containing from 0.05 to 1% by weight of boron and from 40 to 100 free of A composition having a total base number (TBN) expressed on an oil-free basis. The composition according to claim 1, wherein the N-substituted oxalic acid bisamide or amide ester contains a bisamide represented by the formula:

wherein at least two of R ¹ , R ² , R ³ and R ⁴ are independently a group containing a hydrocarbyl group having 12 to 22 carbon atoms, and among the R ¹ , R ² , R ³ and R ⁴ groups 2 or less are independently hydrogen or a hydrocarbyl group of 10 or fewer carbon atoms. The composition according to claim 1, wherein the N-substituted oxalic acid bisamide or amide ester contains a bisamide represented by the formula:

wherein each R ¹ and R ² is independently an alkyl group of 12 to 18 carbon atoms. The composition according to claim 1, wherein the N-substituted oxalic acid bisamide or amide-ester contains an amide-ester represented by the formula:

wherein R ¹ and R ² are independently a hydrocarbyl group having 12 to 22 carbon atoms, and R ¹⁰ is a hydrocarbyl group having 1 to 22 carbon atoms. The composition according to claim 1, wherein (b) the N-substituted oxalic acid bisamide or amide ester contains a bisamide represented by the formula:

wherein each R ⁵ and R ⁷ is independently a hydrocarbyl group having 12 to 22 carbon atoms, and each R ⁶ and R ⁸ is independently hydrogen or a hydrocarbyl group having 1 to 22 carbon atoms. The composition of claim 1, wherein in the amide or thioamide of (c), each R ¹ and R ² is independently a 2-ethylhexyl group or a group having 10 to 18 carbon atoms. The composition of claim 1 , wherein component (c) is an amide among the amides or thioamides. 2. The substituted nitrogen moiety of claim 1, wherein (c) the amide or thioamide contains a di-cocoalkylamine moiety or a (2-ethylhexyl)(hydrogenated tallow)amine moiety. R ¹ R ² N- and a carboxy moiety containing a glycol-based moiety —C(O)R ³ . 3. The method of claim 2, wherein (d) the dispersant component comprises: a first borated succinimide dispersant component having a boron content of 0.1 to 1% by weight and a total base number (TBN) expressed on an oil-free basis of 50 to 100; and a second succinimide dispersant component having a boron content of less than 0.1% by weight and a total base number (TBN) expressed on an oil-free basis of 40 to 80. 11. The composition of claim 10, wherein the second succinimide dispersant component is boron-free. 3. The composition of claim 2, wherein the (d) dispersant component contains at least one succinimide dispersant that reacts with at least one of terephthalic acid or an inorganic phosphorous compound or a dimercaptothiadiazole compound. The friction according to claim 1, wherein a detergent, an antioxidant, a corrosion inhibitor, a seal expander, an antiwear agent, an organic borate ester, an organic borate salt, an antifoam, a viscosity improver or a friction different from that of the component (b) or the component (c). A composition further comprising one or more of a modulating agent. A composition prepared by mixing the components according to claim 1. A method of lubricating a device with a lubricated clutch comprising the step of supplying the composition according to claim 1 . 16. The method of claim 15, wherein the device comprises an automatic transmission.