CA2953823C - Lubricating compositions including mixtures of friction modifiers comprising an n-substituted oxalic acid bisamide or amide-ester containing at least two hydrocarbyl groups, and an amide or thioamide - Google Patents

Abstract

Mixtures of friction modifiers provide excellent friction performance to transmission fluids, where the friction modifiers include an N-substituted oxalic acid bisamide or amide-ester containing at least two hydrocarbyl groups of 12 to 22 carbon atoms; and an amide or thioamide represented by R1R2N-C(X)R3 where X is O or S, R1 and R2 are hydrocarbyl groups of at least 6 carbon atoms, and R3 is hydroxyalkyl group of 1 to 6 carbon atoms or a condensate thereof.

Description

LUBRICATING COMPOSITIONS INCLUDING MIXTURES OF FRICTION MODIFIERS COMPRIS-ING AN N-SUBSTITUTED OXALIC ACID BISAMIDE OR AMIDE-ESTER CONTAINING AT
LEAST TWO HYDROCARBYL GROUPS, AND AN AMIDE OR THIOAMIDE
BACKGROUND
[0001] The disclosed technology relates to additives and fluids for transmissions such as automatic transmission fluids.

[0002] In the automatic transmission marketplace, where there is rapid engineering change driven by the desire to reduce weight and increase transmission capacity, there is a desire for automatic transmission fluids that exhibit a high static coefficient of friction for improved clutch holding capacity. Continuously slipping torque converter clutches, for instance, impose exacting friction requirements on automatic transmission fluids (ATFs). The fluid must have a good friction versus sliding speed relationship, or an ob-jectionable phenomenon called shudder will occur in the vehicle. Transmission shudder is a self-excited vibrational state commonly called "stick-slip" or "dynamic frictional vi-bration" generally occurring in slipping torque converter clutches. The friction charac-teristics of the fluid and material system, combined with the mechanical design and con-trols of the transmission, determine the susceptibility of the transmission to shudder.
Plotting the measured coefficient of friction ( ) versus sliding speed (V), commonly called a -V curve, has been shown to correlate to transmission shudder. Both theory and experiments support the region of positive to slightly negative slope of this -V
curve to correlate to good anti-shudder performance of transmission fluids. A
fluid which allows the vehicle to operate without vibration or shudder is said to have good "anti-shudder" performance. The fluid should maintain those characteristics over its ser-vice lifetime. The longevity of the anti-shudder performance in the vehicle is commonly referred to as "anti-shudder durability." The variable speed friction tester (VSFT) measures the coefficient of friction with respect to sliding speed simulating the speeds, loads, and friction materials found in transmission clutches and correlates to the perfor-mance found in actual use. The procedures are well documented in the literature; see for example Society of Automotive Engineers publication #941883. It is also desirable to obtain good torque capacity in an automatic transmission with wet clutches by providing a lubricant with good frictional performance.

[0003] The combined requirements of high static coefficient of friction and durable positive slope are often incompatible with traditional ATF friction modifier technology which is extremely well described in the patent literature. Many of the commonly used Date recue / Date received 2021-12-02 friction modifiers result in a low static coefficient of friction and are not durable enough on positive slope to be of sufficient use.

[0004] U.S. Patent 8,691,740, Vickerman et al., April 8, 2014, discloses a composi-tion suitable for use as a friction modifier for an automatic transmission, comprising an N-substituted oxalic acid bisamide or amide-ester containing at least two hydro-carbyl groups of 12 to 22 carbon atoms. Other, supplemental friction modifiers may also be present. Other materials that may also be present include antiwear agents such as, among others, various long-chain derivatives of hydroxy carboxylic acids, such as tartrates, tartramides, tartrimides, and citrates.

[0005] U.S. Patent 8,148,306, Bartley et al., April 3, 2012, discloses products of amines with hydroxy acid as friction modifiers suitable for automatic transmission flu-ids. An example is an amide or thioamide represented by the formula R1R2N C(X)R3 wherein X is 0 or S, R1 and R2 are each independently hydrocarbyl groups of at least 6 carbon atoms, and R3 is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by the condensation of said hydroxyalkyl group, through a hydroxyl group thereof, with an acylating agent.

[0006] U.S. Patent 8,450,255, Sumiejski et al., May 28, 2013, discloses a friction modifier comprising at least two hydrocarbyl groups attached to a polar group or atom (e.g., a nitrogen atom), the friction modifier being (a) the reaction product of at least one carboxylic acid or equivalent with at least one aminoalcohol, (b) the reaction product of at least one carboxylic acid or equivalent with at least one polyamine, (c) an amide or thioamide represented by the formula R1R2N¨C(X)R3 wherein X is 0 or S, R1 and are each independently hydrocarbyl groups of at least about 6 carbon atoms, and RI is a hydroxyalkyl group of 1 to about 6 carbon atoms or a group formed by the condensation .. of the hydroxyalkyl group, through a hydroxyl group thereof, with an acylating agent, (d) at least one tertiary amine containing two hydrocarbyl groups and a polyhydroxyl-containing alkyl group or a polyhydroxyl-containing alkoxyalkyl group, or (e) a mixture of two or more of (a), (b), (c) and (d).
SUMMARY

[0007] The disclosed technology provides a composition comprising: (a) an oil of lubricating viscosity; (b) 0.05 to 3.0 percent by weight (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 at least two hydrocarbyl groups of about 12 to about 22 (or 12 to 20 or 12 to 18 or 12 to 16 or 12 to 14 or 14 to 20 or 14 to 18 or 14 to 16) carbon atoms carbon atoms; and (c) 0.05 to 3.0 percent by weight (or 0.1 to 2 or 0.3 to 1 or about 0.7%) of an amide or thioamide repre-sented by the formula R1R2N-C(X)R1 wherein X is 0 or S, R1 and R2 are each inde-pendently hydrocarbyl groups of at least 6 (or 8 to 24 or 10 to 18) carbon atoms, and R3 is hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by the condensation of said .. hydroxyalkyl group, through a hydroxyl group thereof, with an acylating agent.

[0008] In one embodiment the composition further comprises (d) 1 to 6 percent by weight (or 2 to 5.5 or 3 to 5 percent) of a dispersant component, comprising one or more succinimide dispersants, said dispersant component containing 0.05 to 1 percent by weight (or 0.1 to 0.5 or 0.2 to 0.4 percent) boron and having a TBN (oil free) of 40 to 90 (or 45 to 70 or 50 to 68).

[0009] It is desirable for an automatic transmission fluid to have a high quasi-static friction (described in greater detail below), ideally higher than the commonly attained value of about 0.092, without increasing the static friction (again described in greater de-tail below) to a value greater than about 0.135. Moreover, it is desired that these values be stable over time, that is, that they show minimal decrease in friction coefficient from the value at 500 test cycles extending out to 2500 or 10,000 cycles. The good performance should ideally persist over the range of transmission operating temperatures.
Meeting these goals will help provide a fluid that has the properties of good torque capacity, an-tishudder performance, and durability. The materials of the present invention will be suit-able for meeting one or more of these objectives.
DETAILED DESCRIPTION OF THE INVENTION

[0010] Various features and embodiments will be described below by way of non-limiting illustration.

[0011] One component which is used in certain embodiments of the disclosed tech-nology is an oil of lubricating viscosity. Such oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined and re-refined oils and mixtures thereof.

[0012] Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.

[0013] Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
Purifica-tion techniques are known in the art and include solvent extraction, secondary distilla-tion, acid or base extraction, filtration, percolation and the like.

[0014] Re-refined oils are also known as reclaimed or reprocessed oils, and are ob-tained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown prod-ucts.

[0015] Natural oils useful in making the inventive lubricants include animal oils, veg-etable oils (e.g., castor oil,), mineral lubricating oils such as liquid petroleum oils and sol-vent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof

[0016] Synthetic lubricating oils are useful and include hydrocarbon oils such as pol-ymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and mix-tures thereof; alkyl-benzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylben-zenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof

[0017] Other synthetic lubricating oils include polyol esters (such as Pri-olube 3970), dicsters, liquid esters of phosphorus-containing acids (e.g., tricresyl phos-phate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions and typi-cally may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodi-ment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.

[0018] Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows: Group I (sulfur 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 (sulfur content <0.03 wt %, and >90 wt %
saturates, viscosity index >120); Group IV (all polyalphaolefins (PA0s)); and Group V
(all others not included in Groups I, II, III, or IV). The oil of lubricating viscosity may also be an API Group II+ base oil, which term refers to a Group II base oil having a viscosity index greater than or equal to 110 and less than 120, as described in SAE
publication "Design Practice: Passenger Car Automatic Transmissions", fourth Edition, AE-29, 2012, page 12-9, as well as in US 8,216,448, column 1 line 57.

[0019] The oil of lubricating viscosity may be an API Group IV oil, or mixtures thereof, i.e., a polyalphaolefin. The polyalphaolefin may be prepared by metallocene catalyzed processes or from a non-metallocene process.

[0020] The oil of lubricating viscosity comprises an API Group I, Group II, Group 5 III, Group IV, Group V oil or mixtures thereof.

[0021] Often the oil of lubricating viscosity is an API Group I, Group II, Group II+, Group III, Group IV oil or mixtures thereof. Alternatively the oil of lubricating viscosity is often an API Group II, Group II+, Group III or Group IV oil or mixtures thereof. Al-ternatively the oil of lubricating viscosity is often an API Group II, Group II+, Group III
oil or mixtures thereof.

[0022] The amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the additive as de-scribed herein above, and the other performance additives.

[0023] The lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention is in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of components of the invention to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.

[0024] The present technology provides, as one component, an N-substituted oxalic acid bisamide or amide-ester containing at least two hydrocarbyl groups of 12 to 22 car-bon atoms. In certain embodiments, the compound does not contain a primary amine group. (This may be absent in any of the embodiments whatever the detailed chemical nature, and in the presence or absence of other components.) This material is useful as a friction modifier, particularly for lubricating automatic transmissions. This component, as the bisamide, may be represented by the formula m /R3

[0025] In this structure at least two of the Rs are independently groups comprising a hydrocarbyl group of 1 to 22 carbon atoms and up to two of the R groups are hydrogen or a hydrocarbyl group of 10 or fewer carbon atoms. In other embodiments, one or more of the R groups may independently contain 12 to 20 or 12 to 18 or 12 to 16 or 12 to 14 or 14 to 20 or 14 to 18 or 14 to 16 carbon atoms. If there are two hydrocarbyl groups of 12 to 22 carbon atoms, they may be both on the same nitrogen or they may be on differ-ent nitrogen atoms; that is, either R3 and R4 or alternatively Wand R4 may be hydrogen.
The hydrocarbyl groups may be the same or different within a given molecule or within a mixture of molecules in the overall composition.

[0026] Since at least two of the groups RI, R2, R3 and R4 comprise a hydrocarbyl group of 12 to 22 carbon atoms, such groups may be such a hydrocarbyl group, for instance, an al-kyl group of 12 to 22 carbon atoms. Alternatively, such groups may comprise such a hydro-carbyl group as a part of a larger structure. That is, such groups may have the general struc-ture such as R5R6N-R9¨ where one or both of the R5 and R6 are hydrocarbyl groups of 12 to 22 carbons and optionally one of the R5 and R6 may be hydrogen or a shorter hydrocarbyl group. R9 would be a hydrocarbylene linking group, such as methylene, ethylene, propyl-ene, or butylene, and in some cases a 1-3-propylene group. In certain embodiments the alkyl groups of 12 to 22 carbon atoms may contain both linear and cyclic species, e.g., up to 20 percent cyclic species.

[0027] In some embodiments, therefore, the substituted oxalic acid bisamide may comprise a material of the structure about in which two of the groups R1, R2, R4, and R4 are independently alkyl groups of 12 to 22 carbon atoms. Such materials may have a structure such as wherein each R1 and R2 is independently an alkyl group of, for example, 12 to 18 carbon atoms. Such a material may be obtained or obtainable by known methods such as the process of reacting a dialkylamine with an alkyl oxamate such as ethyl oxamate.

[0028] In another embodiment, the N-substituted oxalic acid bisamide or amide-ester comprises an amide-ester represented by the formula:

N

In this embodiment, each R1 and R2 may independently be a hydrocarbyl group of 12 to 22 carbon atoms, as defined elsewhere herein, and R1 may be a hydrocarbyl group of 1 to 22 carbon atoms. In certain embodiments, R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl.

[0029] Long chain monoalkyl and dialkyl amines are commercially available.
The hydrocarbyl group or groups of the amines may be described as long chain hydrocarbyl groups, by which is meant generally hydrocarbyl groups containing 12 to 22 carbon at-oms. For monoalkyl amines, that is, primary amines, the hydrocarbyl group may com-prise a mixture of individual groups on different molecules having a variety of carbon numbers falling generally within the range of 12 to 22 carbon atoms, although molecules with hydrocarbyl groups falling outside this range may also be present. If a mixture of hydrocarbyl groups is present, they may be primarily of even carbon number (e.g., 12, 14, 16, 18, 20, or 22) as is characteristic of groups derived from many naturally-occur-ring materials, or they may be a mixture of even and odd carbon numbers or, alterna-tively, an odd carbon number or a mixture of odd numbers. They may be branched, lin-ear, or cyclic and may be saturated or unsaturated, or combinations thereof.
In certain embodiments the hydrocarbyl groups may contain 16 to 18 carbon atoms, and some-times predominantly 16 or predominantly 18. Specific examples include mixed "coco"
groups, that is, cocoalkyl groups, from cocoamine (predominantly C12 and C14 amines) and mixed "tallow" groups, that is, tallowalkyl groups, from tallowamine (predomi-nantly C16 and C18 groups), and isostearyl groups. The tallow groups may optionally be hydrogenated. Likewise, dialkyl amines, that is, secondary amine, are commercially available, which may have one long chain alkyl group as described above and one short chain alkyl group of 1 to 10 carbon atoms, or which may have two long chain alkyl groups. Examples of the latter include dicocoamine (available as Armeen 2CTm), and ditallowamine. Others, such is isostearyl-coco amine may be synthesized generally as described for preparative example B below.

[0030] It is also contemplated that two or more of the groups R', R2, R3, and R4 may be independently N-hydrocarbyl-substituted or di-substituted aminoalkyl groups wherein the hydrocarbyl substituent or substituents contain 12 to 22 carbon atoms and the alkyl moieties contain 1 to 4 carbon atoms. A formula representing this general structure may be represented by wherein R5 and le are independently a hydrocarbyl group of about 12 to about 22 car-bon atoms and le and le are independently hydrogen or a hydrocarbyl group of 1 to 22 carbon atoms, e.g., a hydrocarbyl group of 10 or fewer carbon atoms or a hydrocarbyl group of about 12 to about 22 carbon atoms. Diamines suitable for preparing such prod-ucts include those in the DuomeenTM series, available from Akzo, having a general structure such as , Such polyamines may be prepared by the addition of the monoamine leleNH to acrylo-nitrile, to prepare the alkyl nitrile amine, V
followed by catalytic reduction of the nitrile group using, e.g., H2 over Pd/C
catalyst, to give the diamine.

[0031] In a related embodiment, the N-substituted oxalic acid bisamide or amide-es-ter may comprise an amide-ester represented by the formula:

R5.--------_______---N N...- ----Rio wherein R5 and le are independently hydrocarbyl groups of 12 to 22 carbon atoms as .. defined above and le may be a hydrocarbyl group of 1 to 22 carbon atoms, such as me-thyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl.

[0032] Some specific examples of the materials for this component of the disclosed technology include those represented by the following structures:
Date recue / Date received 2021-12-02 Coco-, Coco Coco- Isostearyl (I) 0 (II) 0 Coco Coco (III) 0 0 Tallow Tallow Tallow (IV) Coco NN O¨C2H5 (V) Coc Tallow 0¨CH3 (VI) tallow where coco and tallow are as defined above and isostearyl represents the carbon archi-tecture of isostearic acid.

[0033] The bisamides disclosed herein may be prepared by known techniques such as reaction of the appropriate amine with oxalic acid or a reactive equivalent thereof, such as ethyl oxamide or dimethyl oxalate, as illustrated in the preparative examples of U.S. Patent 8,691,740. The amide-esters may be prepared by reaction of the appropriate amine with a dialkyl oxalate, using a controlled amount of amine (approximating 1:1 mo-lar ratio) or by reacting the amine with the half ester-half chloride (e.g., ethyl 2-chloro-2-oxo-acetate). Minor amounts of the amide-esters may be formed along with the prepara-tion of the bisamides, and the relative amounts may be adjusted by known techniques.

[0034] The amount of the oxalic acid bisamide or amide ester in a fully formulated lubricant may be 0.05 to 3 percent by weight, or 0.1 to 2 percent or 0.3 to 1 percent or 5 about 0.7 percent by weight.

[0035] Another component of the disclosed technology, component (c) is an amide or thioamide (at least one amide or thioamide) represented by the formula R1R2N-C(X)R3 wherein X is 0 or S, R1 and R2 are each independently hydrocarbyl groups of at least about 6 (or 8 to 24 or 10 to 18) carbon atoms, and R3 is hydroxyalkyl 10 group of 1 to about 6 carbon atoms or a group formed by the condensation of said hy-droxyalkyl group, through a hydroxyl group thereof, with an acylating agent.
This com-ponent can be viewed as the condensation product of a secondary amine with a hydroxy acid or thioacid (described below), which can also serve as a friction modifier. The amine will contain substituent hydrocarbyl groups, for example, alkyl groups.
The amine may be represented by the formula R1R2NH wherein R1 and R2 are each inde-pendently a hydrocarbyl group of at least 6 carbon atoms (e.g., 6 to 30 carbon atoms or 8 to 24 carbon atoms or 10 to 20 or 10 to 18 or 12 to 16). The R1 and R2 groups may be linear or branched, saturated or unsaturated, aliphatic, aromatic, or mixed aliphatic and aromatic. In certain embodiments they are alkyl groups and in particular linear alkyl groups. The R1 and R2 groups may be the same or different. A commercial example of a suitable amine is sold under the trade name Armeen 2CTM, which is believed to have two C12 alkyl groups. In one embodiment the amine comprises di-cocoalkyl amine or homol-ogous amines. Di-cocoalkyl amine (or di-cocoamine) is a secondary amine in which the two R groups in the above formula are predominantly C12 groups (although amounts of Cg through C18 are generally also present), derived from coconut oil. In certain embodi-ments, one both of the groups R1 and R2 may be 2-ethylhexyl groups. In one embodi-ment, the amine moiety (or "substituted nitrogen moiety") R1R2N¨ of the amide or thio-amide comprises a (2-ethylhexyl)(hydrogenated tallow) amine moiety, where the "hy-drogenated tallow" moiety is derived from tallow, having predominantly C18 groups. It is understood that commercially available dialkylamines will contain certain amounts of monoalkylamines and/or trialkylamines, and products formed from such commercial materials are contemplated to be within the scope of the present inventions (recognizing that any trialkylamine component would not be expected to be reactive to form an am-ide.)

[0036] The amide or thioamide of the present invention may be viewed as a conden-sation product of the above-described amine with a hydroxy acid or hydroxy thioacid or reactive equivalent thereof. In the instance where X is 0, the amide is a derivative of a hydroxy acid which can be represented by the formula R3COOH. In the hydroxy acid (or hydroxy thioacid, as the case may be) R3 is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by the condensation of such hydroxyalkyl group, through the hydroxyl group thereof, with an acylating agent (which may include a sulfur-containing acylating agent). That is, the ¨OH group on R3 is itself potentially reactive and may condense with additional acidic materials or their reactive equivalents to form, e.g., esters. Thus, the hydroxy acid may be condensed, for instance, with one or more additional molecules of acid such as glycolic acid. An example of a suitable hydroxy acid is glycolic acid, that is, hydroxyacetic acid, HO-CH2-COOH. Glycolic acid is readily commercially available, ei-ther in substantially neat form or as a 70% solution in water. When R3 contains more than 1 carbon atom, the hydroxy group may be on the 1 carbon (a) or on another carbon in the chain (e.g., 13 or co). The carbon chain itself may be linear, branched, or cyclic.

[0037] The amount of component (c) in the compositions of the present invention can be 0.05 to 3.0 percent by weight of the finished fluid formulation.
Alternative amounts include 0.1 percent to 2 percent, or 0.3 percent to 1 percent, or about 0.7 per-cent by weight. In a concentrate, the amounts will be proportionately higher.

[0038] Another component that may be present is a dispersant component, which may comprise either a single dispersant species or multiple dispersant species. The dis-persant may be described as "other than a compound as described above" in the event that some of the compounds described above may exhibit some dispersant characteris-tics. Examples of "carboxylic dispersants," as an example, arc described in many U.S.
Patents including the following: 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433, and 6,165,235.

[0039] Succinimide dispersants, a species of carboxylic dispersants, are prepared by the reaction of a hydrocarbyl -substituted succinic anhydride (or reactive equivalent thereof, such as an acid, acid halide, or ester) with an amine, as described above. The hy-drocarbyl substituent group generally contains an average of at least 8, or 20, or 30, or 35 up to 350, or to 200, or to 100 carbon atoms. In one embodiment, the hydrocarbyl group is derived from a polyalkene. Such a polyalkene can be characterized by an M.
(number av-erage molecular weight, which may also be written as MO of at least 500.
Generally, the polyalkene is characterized by an M. of 500 or 700 or 800 or 900, up to 5000 or to 2500 or to 2000 or to 1500. In another embodiment M. varies from 500 or 700 or 800, to 1200 or 1300. In one embodiment the polydispersity /M.) is at least 1.5.

[0040] The polyalkenes include homopolymers and inter-polymers of polymerizable olefin monomers of 2 to 16 or to 6, or to 4 carbon atoms. The olefins may be monoole-fins such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or a polyolefinic monomer, such as diolefinic monomer, such 1,3-butadiene and isoprene. In one embodi-ment, the polymer is a homo-polymer. An example of a polymer is a polybutene.
In one instance about 50% of the polybutene is derived from isobutylene. The polyalkenes can be prepared by conventional procedures.

[0041] In one embodiment, the succinic acylating agents are prepared by reacting a polyalkene with an excess of maleic anhydride to provide substituted succinic acylating agents wherein the number of succinic groups for each equivalent weight of substituent group is at least 1.3, e.g., 1.5, or 1.7, or 1.8. The maximum number of succinic groups per substituent group generally will not exceed 4.5, or 2.5, or 2.1, or 2Ø
The prepara-tion and use of substituted succinic acylating agents wherein the substituent is derived from such polyolefins are described in U.S. Patent 4,234,435. The succinic acylating agents may be prepared either by a chlorine-assisted route or by a thermal ("ene") reac-tion. These synthetic routes are more fully described in U.S. Patent 7,615,521, see col-umns 3-5.

[0042] The substituted succinic acylating agent can be reacted with an amine, includ-ing those amines described above and heavy amine products known as amine still bot-toms. The amount of amine reacted with the acylating agent is typically an amount to provide a mole ratio of CO:N of 1:2 to 1:0.25, or 1:2 to 1:0.75 or 1:1.4 to 1:0.95. In an-other embodiment the CO:N ratio may be 1:0.2 to 1:0.3, and for this or any of the other ratios the resulting dispersant may be further treated with, e.g., dimercaptothiadiazole. If the amine is a primary amine, complete condensation to the imide can occur.
Varying amounts of amide product, such as the amidic acid, may also be present. If the reaction is, rather, with an alcohol, the resulting dispersant will be an ester dispersant. If both amine and alcohol functionality are present, whether in separate molecules or in the same molecule (as in the above-described condensed amines), mixtures of amide, ester, and possibly imide functionality can be present. These are the so-called ester-amide dis-persants.

[0043] "Amine dispersants" are reaction products of relatively high molecular weight aliphatic or alicyclic halides and amines, such as polyalkylene polyamines. Ex-amples thereof are described in the following U.S. Patents: 3,275,554, 3,438,757, 3,454,555, and 3,565,804.

[0044] "Mannich dispersants" are the reaction products of alkyl phenols in which the alkyl group contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). The materials described in the follow-ing U.S. Patents are illustrative: 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.

[0045] Post-treated dispersants may also be a part of the disclosed technology. They are generally obtained by reacting carboxylic, amine or Mannich dispersants with rea-gents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hy-drocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds such as boric acid (to give "borated dispersants"), phosphorus compounds such as phosphorus acids or anhydrides, or 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. Exemplary materials of these kinds are described in the follow-ing U.S. 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, 3,702,757, and 3,708,422.

[0046] In one embodiment, the dispersant component will be present in an amount of 1 to 6 percent by weight of the lubricant formulation, or alternatively 2 to 5.5 or 3 to 5 percent. These amounts represent the total of the individual dispersants that may be pre-sent, if more than one species is present. In one embodiment, the dispersant component comprises one or more succinimide dispersants. In one embodiment, the succinimide dispersant or dispersants will be borated, that is, boron-containing or reacted with a bo-ron species or borating agent, such that the dispersant component as a whole will con-tain 0.05 to 1 percent by weight boron, or alternatively, 0.1 to 0.7 percent or 0.2 to 0.6 percent. If multiple succinimide dispersants are present, the boron may be contained on or associated with one or more of the dispersants while one or more of the other disper-sants will not be borated. (The form of the reaction or association of the boron with the dispersant species is not intended to be limiting.) The TBN of the overall dispersant component, may be 40 to 100, or 40 to 95, or 40 to 90, or 45 to 70, or 50 to 68, as ex-pressed on an oil-free basis. (TBN, or total base number, is the quantity of acid, ex-pressed in milligrams of KOH per gram of sample, that is required to titrate a sample to the specified end point, and is defined in ASTM D-794.)

[0047] In one embodiment the dispersant component comprises a first borated suc-cinimide dispersant component (that is, one more individual species) having a boron content of about 0.1 to about 1 percent by weight, or 0.3 to 0.8, or 0.5 to 0.7 percent by weight and a TBN, in certain embodiments, of 4 to 90 or 50 to 70. In this embodiment the dispersant component will also comprise a second dispersant component (one or more individual species) that is not borated or is borated to a lesser extent than that of the first dispersant component. The second succinimide dispersant component may thus have a boron content of less than 0.1 percent by weight, or less than 0.05 or 0.01 percent by weight, or may be free of boron. The TBN of the second succinimide dispersant com-ponent may be, in certain embodiments, 40 to 80 or 40 to 70 or 50 to 60.

[0048] In certain embodiments the dispersant component comprises more than one individual dispersant species, e.g., more than one individual succinimide dispersant spe-cies. One or more of these may be a succinimide dispersant that is reacted (or post-treated) with at least one of terephthalic acid, or an inorganic phosphorus compound, or a dimercaptothiadiazole compound. For example, in one embodiment there may be three individual succinimide dispersant species present: one may be treated with boron and terephthalic acid; a second may be treated with boron, terephthalic acid, and dimercap-tothiadiazole, and the third may be treated with none of the post-treatment agents. Many such combinations of individual dispersants will be apparent to the person of skill in the art; such combinations may be selected such that the specified amounts of boron are met for the overall dispersant component.

[0049] Other additives may be present in the lubricants of the disclosed technology.
One component frequently used is a viscosity modifier, also referred to as a viscosity improver. Viscosity modifiers (VM) and dispersant viscosity modifiers (DVM) are well known. Examples of VMs and DVMs may include polymethacrylates, polyacrylates, polyolefins, styrene-maleic ester copolymers, and similar polymeric substances includ-ing homopolymers, copolymers, and graft copolymers. The DVM may comprise a nitro-gen-containing methacrylate polymer, for example, a nitrogen-containing methacrylate polymer derived from methyl methacrylate and dimethylaminopropylamine.

[0050] Examples of commercially available VMs, DVMs and their chemical types may include the following: polyisobutylenes (such as IndopolTM from BP Amoco or ParapolTM from ExxonMobil); olefin copolymers (such as LubrizolTM 7060, 7065, and 7067 from Lubrizol and LucantTM HC-2000L and HC-600 from Mitsui); hydrogenated 5 styrene-diene copolymers (such as ShellvisTM 40 and 50, from Shell and LZ
7308, and 7318 from Lubrizol); styrene/maleate copolymers, which are dispersant copolymers (such as LZ 3702 and 3715 from Lubrizol); polymethacrylates, some of which have dispersant properties (such as those in the ViscoplexTm series from RohMax, the HitecTM
series from Afton, and LZ 7702TM, LZ 7727TM, LZ 7725TM and LZ 7720CTM from Lubri-10 zol); olefin-graft-polymethacrylate polymers (such as ViscoplexTM 2-500 and 2-600 from RohMax); and hydrogenated polyisoprene star polymers (such as ShellvisTM

and 260, from Shell). Also included are AstericTM polymers from Lubrizol (methacrylate polymers with radial or star architecture). Viscosity modifiers that may be used are de-scribed in U.S. patents 5,157,088, 5,256,752 and 5,395,539. The VMs and/or DVMs 15 may be used in the functional fluid at a concentration of up to 20% by weight. Concen-trations of 1 to 12%, or 3 to 10% by weight may be used.

[0051] Another component that may be used in the composition used in the present technology is a supplemental friction modifier. These friction modifiers arc well known to those skilled in the art. A list of friction modifiers that may be used is included in U.S. Patents 4,792,410, 5,395,539, 5,484,543 and 6,660,695. U.S. Patent 5,110,488 dis-closes metal salts of fatty acids and especially zinc salts, useful as friction modifiers. A
list of supplemental friction modifiers that may be used may include:
fatty phosphites borated alkoxylated fatty amines fatty acid amides metal salts of fatty acids fatty epoxides sulfurized olefins borated fatty epoxides fatty imidazolines fatty amines other than the fatty condensation products of carboxylic amines discussed above acids and polyalkylene-polyamines glycerol esters metal salts of alkyl salicylates borated glycerol esters amine salts of alkylphosphoric acids alkoxylated fatty amines ethoxylated alcohols oxazolines imidazolines hydroxyalkyl amides polyhydroxy tertiary amines -- and mixtures of two or more thereof.

[0052] Representatives of each of these types of friction modifiers are known and are commercially available. For instance, fatty phosphites may be generally of the formula (R0)2PHO or (R0)(HO)PHO where R may be an alkyl or alkenyl group of sufficient length to impart oil solubility. Suitable phosphites are available commercially and may be synthesized as described in U.S. Patent 4,752,416.

[0053] Borated fatty epoxides that may be used are disclosed in Canadian Patent No.
1,188,704. These oil-soluble boron- containing compositions may be prepared by react-ing 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 may also be useful as sup-plemental friction modifiers.

[0054] Borated amines that may be used are disclosed in U.S. Patent 4,622,158. Bo-rated amine friction modifiers (including borated alkoxylated fatty amines) may be pre-pared by the reaction of a boron compounds, as described above, with the corresponding amines, including simple fatty amines and hydroxy containing tertiary amines.
The amines useful for preparing the borated amines may include commercial alkoxylated fatty amines known by the trademark "ETHOMEEN" and available from Akzo Nobel, such as bis[2-hydroxyethy1]-cocoamine, polyoxyethylenc[10]cocoamine, bis[2-hydroxyethy1]-soyamine, bis[2-hydroxyethy1]-tallowamine, polyoxyethylenc-[5]tallowamine, bis[2-hy-droxyethyl]oleylamine, bis[2¨hydroxyethyl]octadecylamine, and polyoxyethylene[15]-octadecylamine. Such amines are described in U.S. Patent 4,741,848.

[0055] Alkoxylated fatty amines and fatty amines themselves (such as oleylamine) may be useful as friction modifiers. These amines are commercially available.

[0056] Both borated and unborated fatty acid esters of glycerol may be used as fric-tion modifiers. Borated fatty acid esters of glycerol may be prepared by borating a fatty acid ester of glycerol with a boron source such as boric acid. Fatty acid esters of glyc-erol themselves may be prepared by a variety of methods well known in the art.
Many of these esters, such as glycerol monooleate and glycerol tallowate, are manufactured on a commercial scale. Commercial glycerol monooleates may contain a mixture of 45%
to 55% by weight monoester and 55% to 45% by weight diester.

[0057] Fatty acids may be used in preparing the above glycerol esters; they may also be used in preparing their metal salts, amides, and imidazolines, any of which may also be used as friction modifiers. The fatty acids may contain 6 to 24 carbon atoms, or 8 to 18 carbon atoms. A useful acid may be oleic acid.

[0058] The amides of fatty acids may be those prepared by condensation with ammo-nia or with primary or secondary amines such as diethylamine and diethanolamine. Fatty imidazolines may include the cyclic condensation product of an acid with a diamine or polyamine such as a polyethylenepolyamine. In one embodiment, the friction modifier may be the condensation product of a C8 to C24 fatty acid with a polyalkylene polyamine, for example, the product of isostearic acid with tetraethylenepentamine. The condensation products of carboxylic acids and polyalkyleneamines may be imidazolines or amides.

[0059] The fatty acid may also be present as its metal salt, e.g., a zinc salt. These zinc salts may be acidic, neutral, or basic (overbased). These salts may be prepared from the reaction of a zinc containing reagent with a carboxylic acid or salt thereof. A useful method of preparation of these salts is to react zinc oxide with a carboxylic acid. Useful carboxylic acids are those described hereinabove. Suitable carboxylic acids include those of the formula RCOOH where R is an aliphatic or alicyclic hydrocarbon radical.
Among these are those wherein R is a fatty group, e.g., stearyl, oleyl, linoleyl, or pal-mityl. Also suitable are the zinc salts wherein zinc is present in a stoichiometric excess over the amount needed to prepare a neutral salt. Salts wherein the zinc is present from 1.1 to 1.8 times the stoichiometric amount, e.g., 1.3 to 1.6 times the stoichiometric amount of zinc, may be used. These zinc carboxylates arc known in the art and are de-scribed in U.S. Pat. 3,367,869. Metal salts may also include calcium salts.
Examples may include overbased calcium salts.

[0060] Sulfurized olefins are also well known commercial materials used as friction modifiers. A suitable sulfurized olefin is one which is prepared in accordance with the detailed teachings of U.S. Patents 4,957,651 and 4,959,168. Described therein is a cosul-furized mixture of 2 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. The olefin component may be an ali-phatic olefin, which usually will contain 4 to 40 carbon atoms. Mixtures of these olefins are commercially available. The sulfurizing agents useful in the process of the present invention include elemental sulfur, hydrogen sulfide, sulfur halide plus sodium sulfide, and a mixture of hydrogen sulfide and sulfur or sulfur dioxide.

[0061] Metal salts of alkyl salicylates include calcium and other salts of long chain (e.g. C12 to C16) alkyl-substituted salicylic acids.

[0062] 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 PrimeneTM.

[0063] The amount of the supplemental friction modifier, if it is present, may be 0.1 to 1.5 percent by weight of the lubricating composition, such as 0.2 to 1.0 or 0.25 to 0.75 percent. In some embodiments, however, the amount of the supplemental friction modifier is present at less than 0.2 percent or less than 0.1 percent by weight, for exam-ple, 0.01 to 0.1 percent.

[0064] The compositions of the present technology can also include a detergent. De-tergents as used herein are metal salts of organic acids. The organic acid portion of the detergent may be a sulfonate, carboxylate, phenate, or salicylate. The metal portion of the detergent may be an alkali or alkaline earth metal. Suitable metals include sodium, calcium, potassium, and magnesium. Typically, the detergents are overbased, meaning that there is a stoichiometric excess of metal base over that needed to form the neutral metal salt.

[0065] Suitable ovcrbased organic salts include the sulfonate salts having a substan-tially oleophilic character and which are formed from organic materials.
Organic sul-fonates arc well known materials in the lubricant and detergent arts. The sulfonate com-pound should contain on average 10 to 40 carbon atoms, such as 12 to 36 carbon atoms or 14 to 32 carbon atoms on average. Similarly, the phenates, salicylates, and carbox-ylates have a substantially oleophilic character.

[0066] While the present invention allows for the carbon atoms to be either aromatic or in paraffinic configuration, in certain embodiments alkylated aromatics are employed.
While naphthalene based materials may be employed, the aromatic of choice is the ben-zene moiety.

[0067] Suitable compositions thus include an overbased monosulfonated alkylated benzene such as a monoalkylated benzene. Typically, alkyl benzene fractions are ob-tained from still bottom sources and are mono- or di-alkylated. It is believed, in the pre-sent invention, that the mono-alkylated aromatics are superior to the dialkylated aromat-ics in overall properties.

[0068] It is sometimes desired that a mixture of mono-alkylated aromatics (benzene) be utilized to obtain the mono-alkylated salt (benzene sulfonate) in the present inven-tion. The mixtures wherein a substantial portion of the composition contains polymers of propylene as the source of the alkyl groups may assist in the solubility of the salt. The use of mono-functional (e.g., mono-sulfonated) materials avoids crosslinking of the molecules with less precipitation of the salt from the lubricant. It is also frequently de-sired to use an alkylated benzene prepared by alkylation with an a-olefin.

[0069] The salt may be "overbased." By overbasing, it is meant that a stoichiometric excess of the metal base be present over that required for the anion of the neutral salt.
The excess metal from overbasing has the effect of neutralizing acids which may build up in the lubricant. Typically, the excess metal will be present over that which is re-quired to neutralize the anion at in the ratio of up to 30:1, such as 5:1 to 18:1 on an equivalent basis. Overbased materials arc often carbonated, that is, reacted with carbon dioxide, to aid in the acceptance of an equivalent excess of metal.

[0070] The amount of the overbased salt utilized in the composition is typically 0.025 to 3 weight percent on an oil free basis, such as 0.1 to 1.0 percent. In other em-bodiments, the final lubricating composition may contain no detergent or substantially no detergent or only a low amount of detergent. That is, for a calcium overbased deter-gent for instance, the amount may be such as to provide less than 250 parts per million calcium, e.g., 0 to 250 or 1 to 200 or 10 to 150 or 20 to 100 or 30 to 50 parts per million calcium, or less than any of the foregoing non-zero amounts. This is in contrast with more conventional formulations which may contain sufficient calcium detergent to pro-vide 300 to 600 ppm calcium. The overbased salt usually has up to about 50%
oil and has a TBN range of 10-800 or 10-600 on an oil free basis. Borated and non-borated overbased detergents are described in U.S. Patents 5,403,501 and 4,792,410.

[0071] The compositions of the present invention can also include at least one phos-phorus acid, phosphorus acid salt, phosphorus acid ester or derivative thereof including sulfur-containing analogs in the amount of 0.002-1.0 weight percent. The phosphorus acids, salts, esters or derivatives thereof include phosphoric acid, phosphorous acid, phosphorus acid esters or salts thereof, phosphites, phosphorus-containing amides, phos-phorus-containing carboxylic acids or esters, phosphorus-containing ethers, and mix-tures thereof.

[0072] In one embodiment, the phosphorus acid, ester or derivative can be an or-ganic or inorganic phosphorus acid, phosphorus acid ester, phosphorus acid salt, or de-rivative thereof. The phosphorus acids include the phosphoric, phosphonic, phosphinic, and thiophosphoric acids including dithiophosphoric acid as well as the monothiophos-phoric, thiophosphinic and thiophosphonic acids. One group of phosphorus compounds are alkylphosphoric acid mono alkyl primary amine salts as represented by the formula R'0¨ P ¨ Cr +NH3R3 where R1, R2, R3 are alkyl or hydrocarbyl groups or one of R1 and R2 can be H.
The ma-terials can be a 1:1 mixture of dialkyl and monoalkyl phosphoric acid esters.
Com-pounds of this type are described in U.S. Patent 5,354,484.

[0073] Eighty-five percent phosphoric acid is a suitable material for addition to the 10 fully-formulated compositions and can be included at a level of 0.01-0.3 weight percent based on the weight of the composition, such as 0.03 to 0.2 or to 0.1 percent.

[0074] Other phosphorus-containing materials that may be present include dial-kylphosphites (sometimes referred to as dialkyl hydrogen phosphonates) such as dibutyl phosphite. Yet other phosphorus materials include phosphorylated hydroxy-substituted 15 triesters of phosphorothioic acids and amine salts thereof, as well as sulfur-free hy-droxy-substituted di-esters of phosphoric acid, sulfur-free phosphorylated hydroxy-sub-stituted di- or tri-esters of phosphoric acid, and amine salts thereof. These materials are further described in U.S. patent application US 2008-0182770.

[0075] Other materials can optionally be included in the compositions of the present 20 technology, provided that they are not incompatible with the afore-mentioned required components or specifications. Such materials include antioxidants (that is, oxidation in-hibitors), including hindered phenolic antioxidants, secondary aromatic amine antioxi-dants such as dinonyldiphenylamine as well as such well-known variants as monononyldiphenylamine and diphenylamines with other alkyl substituents such as mono- or di-octyl, 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. Also included may be corrosion in-hibitors such as tolyl triazole and dimercaptothiadiazole and oil-soluble derivatives of such materials. Other optional components include seal swell compositions, such as iso-decyl sulfolane or phthalate esters, which are designed to keep seals pliable.
Also per-missible are pour point depressants, such as alkylnaphthalenes, polymethacrylates, vinyl acetate/fumarate or /maleate copolymers, and styrene/maleate copolymers. Other materi-als are anti-wear agents such as zinc dialkyldithiophosphates, tridecyl adipate, and vari-ous long-chain derivatives of hydroxy carboxylic acids, such as tartrates, tartramides, tartrimides, and citrates as described in US Application 2006-0183647. These optional materials are known to those skilled in the art, are generally commercially available, and are described in greater detail in published European Patent Application 761,805. Also included can be known materials such as corrosion inhibitors (e.g., tolyltriazole, dimer-captothiadiazoles), dyes, fluidizing agents, odor masking agents, and antifoam agents.
Organic borate esters and organic borate salts can also be included.

[0076] The above components can be in the form of a fully-formulated lubricant or in the form of a concentrate within a smaller amount of lubricating oil. If they are pre-sent in a concentrate, their concentrations will generally be directly proportional to their concentrations in the more dilute form in the final blend.

[0077] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well-known to those skilled in the art.
Specifically, it refers to a group having a carbon atom directly attached to the remainder of the mole-cule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups .. include:
¨ hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cyclo-alkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aro-matic substituents, as well as cyclic substituents wherein the ring is completed through an-other portion of the molecule (e.g., two substituents together form a ring);
¨ substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocar-bon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
¨ hetero substituents, that is, substituents which, while having a predominantly hydro-.. carbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. In general, no more than two, or no more than one, heteroatom will be present for every ten carbon at-oms in the hydrocarbyl group; typically, there will be no heteroatoms in the hydrocarbyl group.

[0078] It is known that some of the materials described above may interact in the fi-nal formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, includ-ing the products formed upon employing the composition of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifi-cations and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by admixing the components described above.

[0079] The amount of the phosphorus-containing compound or compounds in the compositions of the present invention may, in certain embodiments, be 0.01 to 2 percent by weight, alternatively, 0.02 to 1 or 0.05 to 0.5 percent by weight.
Correspondingly, the total phosphorus content of the compositions may be, for instance 0.01 to 0.3 percent by weight or 0.003 or 0.03 to 0.20 percent by weight or 0.05 to 0.15 percent by weight, de-pending, of course, on the phosphorus content of the particular compounds that are se-lected. In certain embodiments, the formulations of the disclosed technology may con-tain, or may not contain, phosphorus in the form of a zinc dialkyldithiophosphate. In some embodiments there is less than 0.1 percent or 0.01 percent by weight of a zinc di-alkyldithiophosphate. Such materials may be represented by the formula [(R80)(R90)P(=S)-S-]2¨Zn where R8 and R9 are independently hydrocarbyl groups such as alkyl, cycloalkyl, aralkyl or alkaryl groups having 3 to 20 carbon atoms, or 3 to 16 or 3 to 12 carbon atoms. They are typically prepared by the reaction of one or a mixture of alcohols R8OH
and R9OH, which can be a mixture of a secondary alcohol and a primary alcohol, for instance, iso-propanol and 4-methyl-2-pentanol, with phosphorus pentasulfide to give the acid, fol-lowed by neutralization with zinc oxide.

[0080] When the composition is in the form of a concentrate, the relative amounts of the various components will be proportionately increased, for instance, by a factor such as 10 (except for the oil of lubricating viscosity, which will be correspondingly decreased).

[0081] As used herein, the term "condensation product" is intended to encompass es-ters, amides, imides and other such materials that may be prepared by a condensation re-action of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, irrespective of whether a condensation reaction is actu-ally performed to lead directly to the product. Thus, for example, a particular ester may be prepared by a transesterification reaction rather than directly by a condensation reac-tion. The resulting product is still considered a condensation product.

[0082] The amount of each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated. However, unless other-wise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, deriva-tives, and other such materials which are normally understood to be present in the com-mercial grade.

[0083] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well-known to those skilled in the art.
Specifically, it refers to a group having a carbon atom directly attached to the remainder of the mole-cule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substitu-ents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocar-bon groups which, in the context of this invention, do not alter the predominantly hydro-carbon nature of the substituent; and hetero substituents, that is, substituents which simi-larly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain. A more detailed definition of the term "hydrocarbyl substituent" or "hydro-carbyl group" is found in paragraphs [0137] to [0141] of published application 0197536 .

[0084] It is known that some of the materials described above may interact in the fi-nal formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, includ-ing the products formed upon employing the composition of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifi-cations and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by admixing the components described above.

[0085] The invention herein is useful for providing good friction performance to transmission fluids, which may be better understood with reference to the following ex-amples.
EXAMPLES

[0086] The following formulations are prepared for testing:

[0087] A Starting Lubricant, representing a typical or conventional lubricant for an automatic transmission, is prepared containing the following (each of the components other than oil being presented on an oil-free basis, and all percentages being by weight):
Oil(s) of lubricating viscosity (in an amount to total 100%);
Polymethacrylate viscosity modifier, 3.4%
Pour point depressant, 0.2%
Antiwear agents: 0.28%, including dibutyl phosphite and di(long chain alkyl) phosphite Succinimide dispersants: 4.28%, including borated succinimide dispersant(s) and dimer-captothiadiazole-treated dispersant(s) Seal swell agent: 0.5%
Corrosion inhibitors: 0.06%
Antioxidants: 1.1%, including a hindered phenolic ester antioxidant and an aromatic amine antioxidant Detergents: 0.18% overbased calcium sulfonate detergents (low and high TBN
materials) Conventional friction modifier package: 0.61%, including phosphoric acid (85%), bo-rate ester, polyoxyethylene tallowalkylaminc, hydroxyethyl hcptadecenyl imidazolinc, and a long chain hydroxyalkylamine Small amounts of other conventional additives (including antifoam agents, dye and fra-grance additive(s))

[0088] Example 1 also contains, within the Starting Lubricant, 0.70 percent by weight of the condensation product (amide) of dicocoamine and glycolic acid and 0.70 percent by weight of the bisamide formed by reaction of dimethyl oxalate with and N,N-di(C18 alkyl) propylene-1,3-diamine. (The C18 alkyl groups are characteristic of the structure of isostearic acid.)

[0089] Example 2. The same Starting Lubricant is used as for Example 1, except that the amount of the long chain hydroxyalkylamine is less by an amount of 0.01%, the antioxidant component further comprises 0.4% of a substituted hydrocarbyl sulfide, and the specific small amounts of the other conventional additives are slightly different.
The formulation of Example 2 contains, within the modified Starting Lubricant, 0.70 percent by weight of the bisamide formed by reaction of dimethyl oxalate with and N,N-di(C18 alkyl) propylene-1,3-diamine. (The C18 alkyl groups are characteristic of the structure of isostearic acid.)

[0090] For Reference Examples B (138), C (129), and D (123), similar starting lubri-cants are used, which, however, differ in amounts and compositions of certain of the specific components and amounts, generally indicated as follows:

[0091] Reference Example B (138): amount of antiwear component: 0.28%
5 amount of dispersant component: 3.71%
amount of antioxidant component: 1.5%
amount of detergent component: 0.29%
amount of conventional friction modifier component: 0.51%
Reference Example B (138) also contains 0.60 percent by weight of the bisamide formed 10 by reaction of dimethyl oxalate with and N,N-di(C18 alkyl) propylene-1,3-diamine.

[0092] Reference Example C (129): amount of antiwear component: 0.2%
amount of dispersant component: 3.77%
amount of corrosion inhibitor component: 0.11%
amount of antioxidant component: 1.5%
15 amount of detergent component: 0.23%
amount of conventional friction modifier component: 0.62%
Reference Example C (129) also contains 0.75% by weight of the condensation product (amide) of dicocoaminc and glycolic acid.

[0093] Reference Example D (123): amount of antiwear component: 0.2%
20 amount of dispersant component: 3.99%
amount of corrosion inhibitor component: 0.12%
amount of antioxidant component: 1.5%
amount of detergent component: 0.10%
amount of conventional friction modifier component: 0.57%
25 Reference Example D (123) also contains 0.66 percent by weight of the condensation product (amide) of dicocoamine and glycolic acid.

[0094] The formulations thus prepared are subjected to a friction test involving re-peated engagement and disengagement of lubricated steel clutch plates with paper-based friction disks. The testing is conducted on an SAE No. 2 Universal Wet Friction Material Test Machine or on an equivalent machine according to GK or DKA
specifications. The values of measurements are reported at 500, 2500, and 10,000 disengagement cycles.

[0095] All measurements are made with a lubricant formulation maintained at 100 C.
A first measurement is the "quasi-static" coefficient of friction. For this measurement, at a hot condition, the clutch is broken away immediately after the shift with 10 r.p.m to reach 270 C steel plate temperature. The quasi-static friction coefficient is measured 0.5 sec-onds after breakaway has started and the slip speed has stabilized. A second measurement is for "static" coefficient of friction, which condition is defined as the coefficient of fric-tion immediately after disengagement of the clutch plates, the plates moving at a relative rate of 10 r.p.m. Similarly, dynamic coefficients of friction are reported at 90%, 50%, and 10% slip speeds as the clutch engages.

[0096] Results from the testing is shown in the Table below. For each entry, the rele-vant coefficients of friction are reported, in turn, at 500 cycles (start of test), 2500 cycles (middle of test), and 10,000 cycles (end of test):
rt- quasi-static u- static -90% u-50% u-10%
Ex. 1-both f.m.s 0.106 0.128 0.136 0.135 0.136 (start) 0.103 0.131 0.129 0.127 0.131 (oxalic bisamide (mid- 0.108 0.123 0.130 0.129 0.134 die) and amide (c)) (end) Ex. 2 - both f.m.s 0.109 0.136 0.139 0.137 0.143 (start) 0.102 0.134 0.135 0.128 0.132 (oxalic bisamide (mid- 0.107 0.128 0.132 0.132 0.135 die) and amide (c)) (end) Ref. Ex. B(138) - 0.108 0.160 0.129 0.127 0.133 (start) 0.102 0.157 0.126 0.120 0.126 (with oxalic (mid- 0.099 0.161 0.125 0.115 0.120 die) bisamide) (end) Ref. Ex. C(129) - 0.105 0.154 0.131 0.126 0.130 (start) 0.098 0.158 0.129 0.120 0.125 (with amide (c)) (mid- 0.097 0.158 0.129 0.119 0.122 die) (end) Ref. Ex. D(123) ¨ 0.103 0.133 0.130 0.132 0.131 (start) 0.100 0.134 0.128 0.127 0.129 (with amide (c)) (mid- 0.094 0.107 0.110 0.125 0.125 die) (end)

[0097] The results show that the inventive examples, containing both the oxalic bis-amide and the amide of component (c), exhibit superior friction performance properties that remain relatively stable from 500 to 10,000 cycles in the test. The quasi-static coef-ficient of friction is a high, stable value of 1.02-1.09. The static coefficient of friction is a stable value that does not substantially exceed 0.135.

[0098] The mention of any document herein is not an admission that such document qualifies as prior art or constitutes the general knowledge of the skilled person in any ju-risdiction. Except in the Examples, or where otherwise explicitly indicated, all numeri-cal quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as op-tionally modified by the word "about." It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Simi-larly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements.

[0099] As used herein, the transitional term "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of "comprising" herein, it is intended that the term also encompass, as alternative embodi-ments, the phrases "consisting essentially of' and "consisting of," where "consisting of' excludes any element or step not specified and "consisting essentially of' permits the in-clusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration. The expression "consisting of' or "consisting essentially of," when applied to one element of a Date recue / Date received 2021-12-02 claim, is intended to restrict all species of the type represented by that element, notwith-standing the presence of "comprising" elsewhere in the claim.

[0100] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. In this regard, the scope of the invention is to be limited only by the following claims. In certain jurisdictions, recitation of one or more of nar-rower values for a numerical range or recitation of a narrower selection of elements from a broader list means that such recitations represent preferred embodiments.

Claims (16)

What is claimed is:

1. A composition comprising:
(a) an oil of lubricating viscosity;
(b) about 0.05 to about 3.0 percent by weight, 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 at least two hydrocarbyl groups of 12 to 22 or 12 to 20 or 12 to 18 or 12 to 16 or 12 to 14 or 14 to 20 or 14 to 18 or 14 to 16 carbon atoms; and (c) about 0.05 to about 3.0 percent by weight, or 0.1 to 2, or 0.3 to 1, or about 0.7%, of an amide or thioamide represented by the formula R1R2N-C(X)R3 wherein X is 0 or S, Rl and R2 are each independently hydrocarbyl groups of at least 6 or 8 to 24 or 10 to 18 carbon atoms, and R3 is hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by the condensation of said hydroxyalkyl group, through a hydroxyl group thereof, with an acylating agent.

2. The composition of claim 1 further comprising (d) about 1 to about 6 percent by weight or 2 to 5.5 or 3 to 5 percent of a dispersant component, comprising one or more succinimide dispersants, said dispersant component containing about 0.05 to about 1 percent by weight or 0.1 to 0.7 or 0.2 to 0.6 percent boron and having a TBN, on an oil-freebasis, of about 40 to about 100, or 40 to 90, or 45 to 70, or 50 to 68.

3. The composition of claim 1 or 2 wherein the N-substituted oxalic acid bisamide or amide ester comprises a bisamide represented by the formula:

m R3 wherein at least two of Rl, R2, R3, and R4are independently groups comprising a hydrocarbyl group of 12 to 22 carbon atoms and up to two of said groups Rl, R2, R3, and R4 are independently hydrogen or a hydrocarbyl group of 10 or fewer carbon atoms.
Date recue / Date received 2021-12-02

4. The composition of claim 1 or 2 wherein the N-substituted oxalic acid bisamide or amide ester comprises a bisamide represented by the formula R1, R-wherein each Rl and R2 is independently an alkyl group of 12 to 18 carbon atoms.

5. The composition of claim 1 or 2 wherein the N-substituted oxalic acid bisamide or amide-ester comprises an amide-ester represented by the formula:

'N------------------ -----Rio wherein Rl and R2 are independently hydrocarbyl groups of 12 to 22 carbon atoms and Rl is a hydrocarbyl group of 1 to 22 carbon atoms.

6. The composition of any one of claims 1 through 3 wherein (b) the N-substituted oxalic acid bisamide or amide ester comprises a bisamide represented by the formula IR6 -irN N
N N

wherein each of R5 and le is independently a hydrocarbyl group of 12 to 22 carbon atoms and each of R6 and le is independently hydrogen or a hydrocarbyl group of 1 to 22 carbon atoms.
Date recue / Date received 2021-12-02

7. The composition of any one of claims 1 through 6 wherein in (c), the amide or thioamide, each of Rl and R2 is independently a 2-ethylhexyl group or a group of 10 to 18 carbon atoms.

8. The composition of any one of claims 1 through 7 wherein in (c), the amide or thioamide, is an amide.

9. The composition of any one of claims 1 through 8 wherein (c), the amide or thioamide, comprises a substituted nitrogen moiety, R1R2N¨, comprising a di-cocoalkylamine moiety or a (2-ethylhexyl)(hydrogenated tallow)amine moiety and a carboxy moiety, -C(0)R3, comprising a glycolic moiety.

10. The composition of claim 2 wherein (d), the dispersant component, comprises a first borated succinimide dispersant component having a boron content of about 0.1 to about 1 percent by weight or 0.3 to 0.8 or 0.5 to 0.7 and a TBN, on an oil-free basis, of about 50 to about 100 or 70 to 90; and a second succinimide dispersant component having a boron content of less than 0.1 percent by weight and a TBN, on an oil-free basis, of about 40 to about 80 or 40 to 70 or 50 to 60.

11. The composition of claim 10 wherein the second succinimide dispersant component is boron-free.

12. The composition of claim 2 wherein (d), the dispersant component, comprises at least one succinimide dispersant that is reacted with at least one of terephthalic acid or an inorganic phosphorus compound or a dimercaptothiadiazole compound.

13. The composition of any one of claims 1 through 12 further comprising at least one of detergents, antioxidants, corrosion inhibitors, seal swell agents, anti-wear agents, organic borate esters, organic borate salts, anti-foam agents, viscosity improvers, or friction modifiers other than those of component (b) or component (c).

14. A composition prepared by admixing the components as claimed in any one of claims 1 through 13.
Date recue / Date received 2021-12-02

15. A method for lubricating a device with a lubricated clutch comprising supplying thereto the composition as claimed in any one of claims 1 through 14.

16. The method of claim 15 wherein the device comprises an automatic transmission.
Date recue / Date received 2021-12-02