JP6100243B2 - Aromatic imides and esters as lubricating additives - Google Patents

Description

  The technology of the present invention includes automatic transmission fluid, traction fluid, continuously variable transmission fluid (CVT) fluid, two-clutch automatic transmission fluid, agricultural tractor fluid, engine lubricant, industrial gear lubricant, grease, and It relates to the field of additives for fluids such as hydraulic fluids, and lubricants such as engine oils.

  In the automatic transmission market with rapid technological changes driven by the desire to reduce weight and increase transmission capability, automatic transmission fluids with high static coefficient of friction for improved clutch gripping force are desired. ing. For example, a continuously slipping torque converter clutch places severe friction requirements on automatic transmission fluid (ATF). The fluid must have a good friction versus sliding speed relationship, otherwise an undesirable phenomenon called shudder occurs in the vehicle. A transmission shudder is a self-excited vibration state also commonly referred to as “stick slip” or “dynamic frictional vibration” that occurs in a slip torque converter clutch. The friction characteristics of the fluid and material system, combined with the mechanical design and control of the transmission, determine the sensitivity of the transmission to the shudder. A plot of measured coefficient of friction (μ) vs. slip speed (V), commonly referred to as a μ-V curve, has been shown to correlate with transmission shudder. Both theory and experiment support that the positive to slightly negative slope region of this μ-V curve correlates with good anti-shudder performance of the transmission fluid. A fluid that can operate a vehicle without vibrations or shudder is said to have good anti-shudder performance. The fluid must maintain these properties over its service life. The life of shudder resistance in a vehicle is generally referred to as “shudder resistance”. The Variable Speed Friction Tester (VSFT) measures the coefficient of friction with respect to the speed, load and sliding speed that simulates the friction material found in the transmission clutch and correlates with the performance found in actual use. Such procedures are well documented in the literature; see, for example, Society of Automotive Engineers publication # 941883.

  The combined requirement of a high static coefficient of friction and a sustained positive slope is often incompatible with the traditional ATF friction modifier technology which is very well described in the patent literature. Many of the commonly used friction modifiers provide a low static coefficient of friction and do not have enough positive gradient durability for practical use.

  U.S. Pat. No. 6,057,028, 2010, discloses condensation products of hydroxy-polycarboxylic acids and N, N-di (hydrocarbyl) alkylene-diamines, wherein each hydrocarbyl group is independently 1- Contains 22 carbon atoms. The product can be an amide or imide.

  On Feb. 28, 2008, Li, US Pat. No. 6,057,038 contains at least: (a) a major amount of an ester of a polycarboxylic acylating agent; and (b) (i) a metal hydrocarbyl dithiophosphate A lubricating composition containing one compound is disclosed. This composition is suitable for high temperature engines. The polycarboxylic acid acylating agent can be pyromellitic acid, among others.

  On December 2, 1980, Barrer, U.S. Patent No. 5,677,077 discloses tartarimides and lubricants and fuels containing them. In Example (IX), it is reported that the automatic transmission fluid contains the reaction product of tartaric acid and Armeen O (essentially oleylamine).

  On August 16, 2006, Kocsis et al., U.S. Patent No. 5,677,086, discloses tartrate, tartarimide, tartaramide, or combinations thereof useful as additives for lubricants. Various compositions containing automatic transmission fluid are said to benefit from them. Among the materials disclosed are oleyl tartarimide and tridecylpropoxyamine tartarimide. The alkyl group of the amine can be linear or branched.

On December 6, 1988, Horodysky, U.S. Patent No. 5,677,077 discloses a lubricant containing an N-alkylalkylenediamine amide. Disclosed is ^{R 2 -N (R 3) -R} 1 -NH-R 3, wherein, ^{R 1} is _C 2 -C ₄ alkylene group, ^{R 2} is _C 12 _{-C 30} hydrocarbyl R ³ is H, C ₁ -C ₃ aliphatic group or R ⁴ —C (═O) —; at least one of R ³ is R ⁴ —C (═O) — Must. R ⁴ is H or C _1-4 . One example here -NH- _{(CH 2)} a 3 -NH-C (= O) H.

  On May 17, 1966, Hoke, US Pat. In an example, the reactant may be a reaction of xylyl-stearic acid or heptylphenyl-heptanoic acid with tetraethylenepentamine or dodecylamine or N-2-aminoethyloctadecylamine. One example is the condensation product of N-2-aminoethyloctadecylamine and xylyl-stearic acid.

  On January 1, 2009, Watts et al., US Pat. No. 6,087,096, among other ingredients, includes a polyalkylene polyamine based friction modifier that reacts with an acylating agent to convert at least one secondary amine group to an amide. Discloses a lubricating oil composition that is said to have excellent frictional stability.

  Accordingly, the disclosed technology is suitable in certain embodiments to provide a transmission fluid (such as an automatic transmission fluid) having a high coefficient of friction and / or a sustained positive slope in the μ-V curve. A friction modifier is provided.

  There is also a need for lubricants that exhibit anti-wear performance and corrosion inhibition, especially when used to lubricate mechanical devices such as internal combustion engines in formulations characterized by low sulfate ash, phosphorus, and sulfur levels. In certain embodiments, the disclosed technology provides one or more of anti-wear performance and corrosion inhibition when used to lubricate mechanical devices.

International Publication No. WO2010 / 132318 US Patent Application Publication No. 2008/0051307 US Pat. No. 4,237,022 US Patent Application Publication No. 2006/0183647 US Pat. No. 4,789,493 US Pat. No. 3,251,853 US Patent Application Publication No. 2009/0005277

  The disclosed technology has (a) oil of lubricating viscosity and (b) (i) at least two carboxyl groups positioned so as to form a cyclic imide, and 5 or 6 in the cyclic structure. A composition comprising a condensation product of an aromatic polycarboxylic acid having a number of atoms or mixtures thereof or reactive equivalents thereof and (ii) an aliphatic primary amine or alcohol containing 6 to 80 carbon atoms I will provide a.

  In certain embodiments, the aliphatic primary amine or alcohol comprises a primary amine containing 12-60 carbon atoms and further containing a secondary or tertiary amino group or ether group.

式中、Ｒ ^１ およびＲ ^３ のそれぞれは、独立して、約８〜約２２個の炭素原子のアルキル基であり、Ｒ ^２ およびＲ ^４ のそれぞれは、独立して、水素または１〜約２２個の炭素原子のアルキル基であり、但し、Ｒ ^１ およびＲ ^２ 中の総炭素原子数が少なくとも約１３であり、Ｒ ^３ およびＲ ^４ 中の総炭素原子数が少なくとも約１３であることを条件とする；
によって示される材料を含む、項目１〜４、６、７、または９〜１３のいずれか１項に記載の組成物。
（項目１５）
Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ 、およびＲ ^４ が、タローアミン、ココアミン、またはイソステアリルアミンの特徴を示すアルキル基である、項目１４に記載の組成物。
（項目１６）
前記縮合生成物の量が約０．０００１〜約１０重量％である、項目１〜１５のいずれか１項に記載の組成物。
（項目１７）
分散剤、粘度調整剤、補助的摩擦調整剤、清浄剤、酸化防止剤、シール膨潤剤、および摩耗防止剤からなる群から選択される少なくとも１つのさらなる添加剤をさらに含む、項目１〜１６のいずれか１項に記載の組成物。
（項目１８）
有機ホウ酸エステル、有機ホウ酸塩、有機リンのエステル、有機リンの塩、無機リンの塩、および無機リンの酸からなる群から選択される少なくとも１つの添加剤をさらに含む、項目１〜１６のいずれかに記載の組成物。
（項目１９）
機械的デバイスを潤滑する方法であって、項目１〜１８のいずれか１項に記載の組成物を前記デバイスに供給することを含む、方法。
（項目２０）
前記機械的デバイスが変速機を含む、項目１９に記載の方法。
（項目２１）
前記機械的デバイスが自動変速機を含む、項目１９または２０に記載の方法。
（項目２２）
前記機械的デバイスが内燃機関を含む、項目１９に記載の方法。 The disclosed technology further provides a method of lubricating a mechanical device comprising providing any of the above compositions. In certain embodiments, the mechanical device includes an automatic transmission. In certain embodiments, the composition imparts useful friction properties when lubricating an automatic transmission.
In one embodiment, for example, the following items are provided:
(Item 1)
A composition comprising:
(A) oil of lubricating viscosity, and
(B) The following:
(I) an aromatic polycarboxylic acid having at least two carboxyl groups positioned so that a cyclic imide is formed, and having 5 or 6 atoms in the cyclic structure, or a mixture thereof or a reactivity thereof The equivalent,
(Ii) condensation products with aliphatic primary amines or alcohols containing from about 6 to about 80 carbon atoms
A composition comprising:
(Item 2)
Item 1. The aliphatic primary amine or alcohol comprises a primary amine containing from about 12 to about 60 carbon atoms and further containing a secondary or tertiary amino group or ether group. The composition as described.
(Item 3)
The composition of item 1, wherein the condensation product comprises an ester, an amide, an imide, or an imidazoline.
(Item 4)
Item 4. The composition according to any one of Items 1 to 3, wherein the condensation product contains a cyclic imide.
(Item 5)
Item 5. The composition of any one of Items 1-4, wherein the aromatic polycarboxylic acid or reactive equivalent thereof comprises an aromatic ring substituted with at least one succinic acid group or reactive equivalent thereof.
(Item 6)
Any of items 1-4, wherein the aromatic polycarboxylic acid or reactive equivalent thereof comprises an aromatic group having at least two carboxylic acid groups or reactive equivalents on at least two aromatic carbon atoms. 2. The composition according to item 1.
(Item 7)
Item 7. The composition according to Item 6, wherein the aromatic polycarboxylic acid or reactive equivalent thereof comprises a benzene ring having at least two carboxylic acid groups or reactive equivalents on adjacent carbon atoms.
(Item 8)
The aromatic polycarboxylic acid or a reactive equivalent thereof includes a naphthalene structure, which includes a naphthalene structure having two carboxylic acid groups arranged at the 1-position and the 8-position of the naphthalene structure or a reactive equivalent thereof. Item 7. The composition according to Item 6.
(Item 9)
Item 9. The composition according to any one of Items 1 to 8, wherein the condensation product contains diimide.
(Item 10)
Item 10. The composition according to any one of Items 1-4, 6, 7, or 9, wherein the condensation product comprises pyromellitic acid diimide.
(Item 11)
The aliphatic primary amine has the formula:
_{H 2 N- (C n H 2n} ) -X-R 1
Where n is 2 to about 6,
X is O or N—R ² ;
R ¹ is an alkyl group of at least about 8 carbon atoms;
R ² is H or an alkyl group;
The composition according to any one of items 1 to 10, which is represented by:
(Item 12)
Item 12. The composition according to any one of Items 1 to 11, wherein the aliphatic primary amine comprises N, N-dialkyl-1,3-propanediamine.
(Item 13)
The N, N-dialkyl-1,3-propanediamine is N, N-di- (hydrogenated tallow) -1,3-propanediamine, N, N-dicoco-1,3-propanediamine, or N, Item 13. The composition according to Item 12, comprising N-diisostearyl-1,3-propanediamine.
(Item 14)
The condensation product is

Wherein each of R ¹ and R ³ is independently an alkyl group of about 8 to about 22 carbon atoms, and each of R ² and R ⁴ is independently hydrogen or 1 to about 22 An alkyl group of carbon atoms provided that the total number of carbon atoms in R ¹ and R ² is at least about 13 and the total number of carbon atoms in R ³ and R ⁴ is at least about 13 And
14. A composition according to any one of items 1-4, 6, 7, or 9-13, comprising a material represented by
(Item 15)
Item 15. The composition according to Item 14, wherein R ¹ , R ² , R ³ , and R ⁴ are alkyl groups exhibiting characteristics of tallow amine, coco amine, or isostearyl amine.
(Item 16)
16. A composition according to any one of items 1 to 15, wherein the amount of the condensation product is from about 0.0001 to about 10% by weight.
(Item 17)
Items 1-16, further comprising at least one additional additive selected from the group consisting of dispersants, viscosity modifiers, auxiliary friction modifiers, detergents, antioxidants, seal swell agents, and antiwear agents. The composition according to any one of the above.
(Item 18)
Items 1-16, further comprising at least one additive selected from the group consisting of an organic borate, an organic borate, an organic phosphorus ester, an organic phosphorus salt, an inorganic phosphorus salt, and an inorganic phosphorus acid The composition in any one of.
(Item 19)
A method of lubricating a mechanical device, comprising providing the device with a composition according to any one of items 1-18.
(Item 20)
20. A method according to item 19, wherein the mechanical device comprises a transmission.
(Item 21)
21. A method according to item 19 or 20, wherein the mechanical device comprises an automatic transmission.
(Item 22)
20. A method according to item 19, wherein the mechanical device comprises an internal combustion engine.

FIG. 1 shows the coefficient of friction over a 30,000 test cycle provided by a lubricant containing pyromellitic diimide of the disclosed technique.

  Various features and embodiments are described below by way of non-limiting illustration.

  One component used in certain embodiments of the disclosed technology is an oil of lubricating viscosity, which may be present in high amounts for lubricant compositions, and concentrate formation for concentrates. May be present in an amount. Suitable oils include natural and synthetic lubricating oils and mixtures thereof. In fully formulated lubricants, oils of lubricating viscosity are generally present in large amounts (ie, greater than 50% by weight). Typically, the oil of lubricating viscosity is present in an amount from 75 to 95%, often more than 80% by weight of the composition.

  Natural oils useful for making the lubricants and functional fluids of the present invention include animal and vegetable oils and paraffinic, naphthenic or mixed paraffin / mixtures that may be further refined by hydrocracking and hydrofinishing processes. Included are naphthenic liquid petroleum and mineral lubricating oils such as solvent or acid treated mineral lubricating oils.

  Synthetic lubricating oils include polymerized and internally polymerized olefins, also known as polyalphaolefins; polyphenyls; alkylated diphenyl ethers; alkyl or dialkylbenzenes; and alkylated diphenyl sulfides; and hydrocarbon oils such as derivatives, analogs and homologs thereof, and Halo-substituted hydrocarbon oils are included. Also included are alkylene oxide polymers and interpolymers and derivatives thereof in which the terminal hydroxyl groups may be modified by esterification or etherification. Also included are esters of dicarboxylic acids with various alcohols, or esters obtained from C5 to C12 monocarboxylic acids and polyols or polyol ethers. Other synthetic oils include silicon-based oils, liquid esters of phosphorus-containing acids and polymeric tetrahydrofurans.

  Natural or synthetic unrefined, refined and rerefined oils can be used in the lubricants of the present technology (ie, the inventive technology of the present disclosure). Unrefined oils are those obtained directly from natural or synthetic sources without further purification. Refined oils are further processed in one or more purification steps to improve one or more properties. For example, they can be hydrogenated to provide oils with improved stability to oxidation.

  In one embodiment, the oil of lubricating viscosity is an API Group I, Group II, Group III, Group IV or Group V oil or a mixture thereof comprising synthetic oil. In another embodiment, the oil is Group II, III, IV or V. These are classifications established by the API Base Oil Interchangeability Guidelines. Group III oils contain no more than 0.03% sulfur and no less than 90% saturation and have a viscosity index of no less than 120. Group II oils have a viscosity index of 80-120 and contain 0.03% or less sulfur and 90% or more saturation. Polyalphaolefins are classified as Group IV. The oil may be an oil obtained by a hydroisomerization reaction of a wax, such as a slack wax or a Fischer-Tropsch synthetic wax. Such “GTL (Gas-to-Liquid)” oils are generally classified as Group III. Group V includes "all others" (except for Group I, which contains more than 0.03% S and / or less than 90% saturation and has a viscosity index of 80-120).

In one embodiment, at least 50% by weight of the oil of lubricating viscosity is polyalphaolefin (PAO). Typically, polyalphaolefins are derived from monomers having 4 to 30, 4 to 20, or 6 to 16 carbon atoms. Examples of useful PAOs include those derived from 1-decene. These PAOs can have a viscosity of 1.5 to 150 mm ² / sec (cSt) at 100 ° C. PAO is typically a hydrogenated material.

The oils of the present technology can include a single viscosity range oil or a mixture of high and low viscosity range oils. In one embodiment, the oil exhibits a kinematic viscosity at 100 ° C. of 1 or 2-8 or / -10 mm ² / s (cSt). The entire lubricant composition has a viscosity at 100 ° C. of 1 or 1.5-10, ˜15 or ˜20 mm ² / sec, and a Brookfield viscosity at −40 ° C. (ASTM-D-2983) of 20 or It can be blended using oil and other components so as to be less than 15 Pa-s (20,000 cP or 15,000 cP), for example, less than 10 Pa-s, and further 5 Pa-s or less.

  The technology of the present invention is an aromatic polycarboxylic acid having, as one component, at least two carboxyl groups positioned such that a cyclic imide is formed, and having 5 or 6 atoms in the cyclic structure. Condensation products of acids or mixtures thereof or reactive equivalents thereof with aliphatic primary amines or alcohols containing 6 to 60 carbon atoms are provided. As used herein, the term “aliphatic”, in some embodiments, can include both cyclic or acyclic groups (ie, “alicyclic”), and other embodiments Then, it can be limited to an acyclic group. In certain embodiments, these materials are particularly useful as friction modifiers for automatic transmission lubrication. In other embodiments, these materials are particularly useful as antiwear or corrosion inhibitors for internal combustion engine lubrication.

The aromatic polycarboxylic acid or reactive equivalent thereof can be a diacid, triacid, tetraacid, or a higher acid (or reactive equivalent). When the reaction product is a monoimide, the polycarboxylic acid contains at least two acid (or equivalent) groups. When the reaction product is a diimide, the polycarboxylic acid contains at least four acid (or equivalent) groups. The acid group is positioned such that a 5- or 6-membered cyclic imide is formed. This group of the acid is, for example, or can be a cross in the ortho position on the aromatic ring, which may have a other relationships that are described in more detail below (e.g., two carbonyl groups, two adjacent carbon atoms, or, may be bonded to two carbon atoms separated by one atom as a forward, generally, the does not bind) to the position meta to each other on the aromatic ring means. However, this term should not be construed as requiring that the cyclic imide be formed in each case. For example, amides or esters do not form a cyclic imide structure, but the same geometric relationship of the precursor acid groups is applicable.

  Reactive equivalents of carboxylic acids include acids, esters, acid halides such as acid chlorides, and anhydrides. The term “carboxylic acid” can be used herein for the sake of brevity to refer to a carboxylic acid or its reactive equivalent. Due to its availability and ease of reaction, anhydrides, especially cyclic anhydrides, are often used. Cyclic anhydrides are typically considered to constitute a cyclic structure of 5 or 6 atoms, so cyclic anhydrides typically have 5 or 6 carbon atoms in their cyclic structure. It is located so as to form a cyclic imide having. The condensation product of the present technology can have a cyclic imide structure, but is not necessary. The condensation product can contain, for example, an ester group, an amide group, or an imidazoline group. The reaction product of an anhydride and an amine or alcohol is usually referred to as a condensation product, even though small molecules such as water cannot be produced by reaction under the entire environment.

  The carboxylic acid group can be bonded directly to the aromatic group or can be bonded indirectly via an intervening carbon atom. An example of the latter type of material is an aromatic ring substituted with at least one succinic acid (or anhydride) group, optionally with other ring substituents, for example phenyl succinic acid or anhydride. It is.

This material has two carboxyl groups positioned such that a cyclic imide having 5 carbon atoms is formed in the cyclic structure.

  In other embodiments, the aromatic polycarboxylic acid can include an aromatic group having at least two carboxyl groups bonded directly to at least two aromatic carbon atoms. The aromatic group can be a single ring (monocycle) or a fused ring. Carboxylic acid groups can be in adjacent positions on the aromatic ring (eg, ortho to each other) or appropriately positioned on different aromatic rings. Examples include phthalic anhydride, pyromellitic anhydride, and naphthalene-1,8-dioic anhydride. The former has groups on the benzene ring and the latter has groups on the naphthalene (ie, fused) ring. The latter is an example of a material that can form a cyclic imide having two carboxylic acid groups present at the 1- and 8-positions and having 6 atoms in the ring.

  There may be additional substituents on any aromatic ring including additional carboxylic acid groups, hydrocarbyl groups, hydroxy groups, ether groups, and additional aromatic groups, including fused or non-fused rings. . In addition, one carboxyl group can be directly attached to the aromatic ring and the second carboxyl group can be linked via one or more carbon atoms (eg, 2-carboxymethylbenzoic anhydride).

  Aromatic polycarboxylic acids are condensed with primary amines or alcohols containing 6 to 60 carbon atoms. The resulting condensation product type depends on the reactants. When the reactant is an alcohol, the product is either an ester (monoester (ie, partial ester) or polyester (ie, diester, triester, or tetraester, depending on the identity of the aromatic polycarboxylic acid)) ). The polymeric product is not intended for the term “polyester”, but polymeric materials are not necessarily excluded. The ester type depends on the number of equivalents of alcohol to react. As will be apparent to those skilled in the art, when the reactant is a primary amine, the product can also be an amide or imide, depending on the number of equivalents of amine to react and the reaction conditions. In more severe conditions, it is typically necessary to form a cyclic imide. In certain embodiments, the condensation product comprises an imide and, in certain cases, a diimide. In certain embodiments, the condensation product comprises pyromellitic diimide.

  The reaction product can be a condensation product with an aliphatic primary amine or aliphatic alcohol. The product can include an ester, amide, or imide, and the imide can be a cyclic imide. The primary amine or alcohol is 6 to 80 carbon atoms, or 8 to 70 carbon atoms, or 12 to 60 carbon atoms, or 16 to 50 carbon atoms, or 18 to 40 carbon atoms. It can contain atoms. The primary amine or alcohol having any of the above carbon numbers can further comprise a secondary or tertiary amino group or ether group capable of breaking the carbon chain. In some examples, the carbon atom normally located at the 3, 4, 5, 6, or 7 position in the amine or alcohol carbon chain is replaced with an oxygen or nitrogen atom. In some embodiments, the replacement atom is in the 4-position.

In certain embodiments, the product has the formula H ₂ N— (C _n H _2n ) —X—R ¹ , wherein n is 2-6, X is O or N—R ² , R ¹ is an alkyl group of at least 8 or at least 10 carbon atoms, and R ² is H or an alkyl group). R ¹ and R ² groups are alkyl groups containing at least 4 carbon atoms, such as 6-40, or 8-30, or 10-24, or 12-20, or 16-18 carbon atoms, And a mixture of such groups. In certain embodiments, the aliphatic primary amine of the above structure comprises N, N-dialkyl-1,3-propanediamine, such as N, N-di-hydrogenated tallow-1,3-propanediamine. , N, N-dicoco-1,3-propanediamine or N, N-diisostearyl-1,3-propanediamine.

  Hydrocarbyl groups in amines or alcohols may include a mixture of individual groups on the same or different molecules having a variety of carbon numbers generally included within the above carbon number range, but are not included in this range. There may also be molecules having groups. When a mixture of hydrocarbyl groups is present, they are predominantly even numbers of carbon numbers (eg, 12, 14, 16, 18, 20, or 22) that are characteristic of groups derived from many naturally occurring materials. Or they may be a mixture of even and odd carbon numbers, or a mixture of odd or odd carbon numbers. They may be branched, linear or cyclic, saturated or unsaturated, or a combination thereof. In certain embodiments, the hydrocarbyl group can contain 16-18 carbon atoms and can contain predominantly 16 or predominantly 18 carbon atoms. Specific examples include mixed “coco” groups derived from cocoamines (primarily C12 and C14 amines), and mixed “tallow” groups, “isostearyl” groups derived from tallow amines (primarily C16 and C18 groups) (eg, Isooctadecyl group or 16-methylheptadecyl group), and 2-ethylhexyl group.

  Suitable diamines for the preparation of such products include

And the Duomeen ™ series of diamines available from AkzoNobel. Such polyamine is added to monoamine R ¹ R ² NH to acrylonitrile to obtain alkyl nitrile amine (cyanoalkylamine).

Followed by catalytic reduction of the nitrile group with, for example, H ₂ over a Pd / C catalyst to give the diamine.

  Some specific examples of materials of the disclosed technology include the following structure (I):

Is included. In this representation, each of R ¹ and R ³ may independently be an alkyl group of 10 to 22 carbon atoms, and each of R ² and R ⁴ is independently hydrogen or 1-22 An alkyl group of carbon atoms, provided that the total number of carbon atoms in R ¹ and R ² is at least about 13 and the total number of carbon atoms in R ³ and R ⁴ is at least about 13. As a condition. In certain embodiments, R ¹ , R ² , R ³ , and R ⁴ are independently alkyl groups that are characteristic of tallow amines (including hydrogenated “tallow” groups) or cocoamines.

  The amount of condensation product in the fully formulated lubricant may be approximately 0.0001 to 10% by weight. When used to lubricate a transmission, suitable amounts include 0.05 to 10% by weight, 0.1 to 10%, or 0.3 to 5%, or 0.5 to 6%, or 0. 5 to 2.5%, or 0.8 to 4%, or 1 to 2.5%, or 0.8 to 2% is included. When used to lubricate internal combustion engines, suitable amounts include 0.0001-0.1% by weight, or 0.001-0.05%, or 0.002-0.03%.

  Other components may also be present. One such component is a dispersant. If some of the products can exhibit dispersant properties, it can be expressed as “other than the condensation product as described above”. Examples of dispersants are the following US patents: 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, It is described in a number of US patents including 3,632,511, 4,234,435, US Reissue Patent 26,433, and 6,165,235.

  A succinimide dispersant, a type of carboxylic acid dispersant, is prepared by reacting a hydrocarbyl-substituted succinic anhydride (or its reactive equivalent such as an acid, acid halide or ester) with an amine as described above. The Hydrocarbyl substituents generally contain on average at least 8, or 20, or 30 or 35 to 350, or 200 or 100 carbon atoms. In one embodiment, the hydrocarbyl group is derived from a polyalkene. Such polyalkene has at least 500

(Number average molecular weight). Generally, the polyalkene is 500 or 700, or 800 or 900 to 5000, or 2500, or 2000, or 1500.

It is characterized by. In another embodiment,

Varies from 500, or 700 or 800 to 1200 or 1300. In one embodiment, polydispersity

Is at least 1.5.

  Polyalkenes include homopolymers and interpolymers of polymerizable olefin monomers of 2 to 16, or ˜6 or ˜4 carbon atoms. The olefin may be a monoolefin such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or a polyolefin monomer such as a diolefin monomer such as 1,3-butadiene and isoprene. In one embodiment, the interpolymer is a homopolymer. An example of a polymer is polybutene. In one example, about 50% or at least 50% of the polybutene is derived from isobutylene. Polyalkenes can be prepared by conventional procedures.

  In one embodiment, the succinic acylating agent is prepared by reacting a polyalkene with an excess of maleic anhydride to provide a substituted succinic acylating agent. Here, the number of succinic groups for each equivalent of substituents is at least 1.3, such as 1.5, or 1.7 or 1.8. The maximum number of succinic groups per substituent generally does not exceed 4.5, or 2.5, or 2.1 or 2.0. The preparation and use of substituted succinic acylating agents wherein substituents are derived from such polyolefins is described in US Pat. No. 4,234,435.

  Substituted succinic acylating agents can be reacted with amines including the above-described amines and heavy amine products known as amine still bottoms. The amount of amine reacted with the acylating agent is typically an amount that provides a CO: N molar ratio of 1: 2 to 1: 0.25 or 1: 2 to 1: 0.75. When the amine is a primary amine, complete condensation to the imide can be performed. Various amounts of amide product, such as amide acid, can also be present. Rather, when the reaction is with an alcohol, the resulting dispersant is an ester dispersant. If both an amine function and an alcohol function are present, there can be a mixture of amide, ester, and possibly imide functions, either in a separate molecule or in the same molecule (such as the condensed amine described above). These are so-called ester-amide dispersants.

  An “amine dispersant” is the reaction product of a relatively high molecular weight aliphatic or cycloaliphatic halide with an amine, such as a polyalkylene polyamine. Examples are described in the following US patents: 3,275,554, 3,438,757, 3,454,555 and 3,565,804.

  A “Mannic dispersant” is the reaction product of an alkylphenol whose alkyl group contains at least 30 carbon atoms with an aldehyde (especially formaldehyde) and an amine (especially a polyalkylene polyamine). The materials described in the following US patents are exemplary: 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-treatment dispersants are also part of the present technique. They generally contain carboxylic acids, amines or Mannich dispersants, boron compounds such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boric acids, etc. It can be obtained by reacting with a phosphorus compound such as phosphoric acid or its anhydride, or a reagent such as 2,5-dimercaptothiadiazole (DMTD). Examples of this type of material are the following US patents: 3,200,107, 3,282,955, 3,367,943, 3,513,093, 3,639, No. 242, No. 3,649,659, No. 3,442,808, No. 3,455,832, No. 3,579,450, No. 3,600,372, No. 3,702,757 And 3,708,422.

  Mixtures of dispersants can also be used. When present in the inventive formulation, the amount of dispersant is generally from 0.3 to 10% by weight. In other embodiments, the amount of dispersant is 0.5-7%, or 1-10%, or 1-5%, or 1.5-9%, or 2-8% of the final blend fluid formulation. is there. In the concentrate, the amount increases proportionally.

  Another frequently used component is a viscosity modifier. Viscosity modifiers (VM) and dispersant viscosity modifiers (DVM) are well known. Examples of VMs and DVMs can include polymethacrylates, polyacrylates, polyolefins, styrene-maleic acid ester copolymers, and similar polymeric materials including homopolymers, copolymers, and graft copolymers. The DVM can include a nitrogen-containing methacrylate polymer, such as a nitrogen-containing methacrylate polymer derived from methyl methacrylate and dimethylaminopropylamine.

  Examples of commercially available VMs, DVMs and their chemical types include: polyisobutylene (such as Indopol ™ from BP Amoco or Parapol ™ from ExxonMobil); olefin copolymer (Lublizol ™ from Lubrizol) 7060, 7065 and 7067 and Lucant ™ HC-2000L and HC-600 from Mitsui; hydrogenated styrene-diene copolymers (Shellvis ™ 40 and 50 from Shell and LZ® 7308 from Lubrizol). And styrene / maleate copolymers (such as LZ® 3702 and 3715 from Lubrizol); Rate (some of which have dispersant properties) (Viscoplex (TM) series from RohMax, Hitec (TM) series of viscosity index improvers from Afton and LZ7702 (TM), LZ7727 (TM) from Lubrizol) , LZ7725 ™ and LZ7720C ™); olefin-graft-polymethacrylate polymers (such as Viscoplex ™ 2-500 and 2-600 from RohMax); and hydrogenated polyisoprene star polymers (Shellvis from Shell). (Trademarks) 200 and 260, etc.). Also included are Asteric ™ polymers from Lubrizol (methacrylate polymers with radial or star-shaped structures). Viscosity modifiers that can be used are described in US Pat. Nos. 5,157,088, 5,256,752 and 5,395,539. The VM and / or DVM can be used at a concentration of up to 20% by weight in the functional fluid. It can be used at a concentration of 1 to 12% by weight or 3 to 10% by weight.

Another ingredient that can be used in the composition used in the present technique 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 U.S. Pat. Nos. 4,792,410, 5,395,539, 5,484,543, and 6,660,695. US Pat. No. 5,110,488 discloses fatty acid metal salts, particularly zinc salts, useful as friction modifiers. For a list of auxiliary friction modifiers that can be used:
Fatty phosphites Borated alkoxylated fatty amine fatty acid amides Metal salts of fatty acids Fatty epoxides Sulfurized olefins Borated fatty epoxides Fatty imidazolines Fatty amines other than fatty amines discussed above Glycerol esters of carboxylic acids and polyalkylene-polyamines Alkyl Salicylate metal salt Borated glycerol ester Alkyl phosphoric acid amine salt Alkoxylated fatty amine Ethoxylated alcohol oxazoline Imidazoline hydroxyalkylamide Polyhydroxy tertiary amine dialkyl tartrate Molybdenum compound and mixtures of two or more thereof may be included .

Representatives of each of these types of friction modifiers 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 is an alkyl or alkenyl group of sufficient length to impart oil solubility. It may be. Suitable phosphites are commercially available and can be synthesized as described in US Pat. No. 4,752,416.

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

  The borated amines that can be used are disclosed in US Pat. No. 4,622,158. Borated amine friction modifiers (including borated alkoxylated fatty amines) are prepared by reacting boron compounds with the corresponding amines including simple fatty amines and hydroxy containing tertiary amines as described above. be able to. Useful amines for preparing borated amines include commercially available alkoxylated aliphatic amines known by the trade name “ETHOMEEN” and available from Akzo Nobel, such as bis [2-hydroxyethyl] -coco-amine, Polyoxyethylene [10] cocoamine, bis [2-hydroxyethyl] -soyamine, bis [2-hydroxyethyl] -tallow-amine, polyoxyethylene- [5] tallowamine, bis [2-hydroxyethyl] oleyl-amine, Bis [2-hydroxyethyl] octadecylamine and polyoxyethylene [15] octadecylamine may be included. Such amines are described in US Pat. No. 4,741,848.

  Alkoxylated fatty amines and fatty amines themselves (such as oleylamine) can be useful as friction modifiers. These amines are commercially available.

  Both borated and non-borated fatty acid esters of glycerol can be used as friction modifiers. A borated fatty acid ester of glycerol can be prepared by bolating a fatty acid ester of glycerol with a boron source such as boric acid. The fatty acid ester of glycerol itself can be prepared by various methods well known in the art. Many of these esters such as glycerol monooleate and glycerol tallowate are produced on a commercial scale. Commercial glycerol monooleate can contain a mixture of 45% to 55% by weight monoester and 55% to 45% diester.

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

  Fatty acid amides may be prepared by condensation with ammonia or primary or secondary amines such as diethylamine and diethanolamine. The fatty imidazoline can comprise a cyclic condensation product of an acid and a diamine or polyamine, such as a polyethylene polyamine. In one embodiment, the friction modifier may be a condensation product of a C8-C24 fatty acid and a polyalkylene polyamine, such as a product of isostearic acid and tetraethylenepentamine. The condensation product of carboxylic acid and polyalkyleneamine may be an imidazoline or amide.

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

  Sulfurized olefins are also well-known commercial 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. Co-sulfurization 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. Mixtures are described. The olefin component may be an aliphatic olefin usually containing 4 to 40 carbon atoms. Mixtures of these olefins are commercially available. Sulfiding agents useful in the process of the present invention include elemental sulfur, hydrogen sulfide, sulfur halide + sodium sulfide and mixtures of hydrogen sulfide with sulfur or sulfur dioxide.

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

  Alkyl phosphoric acid amine salts include salts of phosphoric acid oleyl esters and other long chain esters with amines such as tertiary aliphatic primary amines marketed under the trade name Primene ™. It is.

  When present, the amount of auxiliary friction modifier may be 0.1-1.5% by weight of the lubricating composition, such as 0.2-1.0 or 0.25-0.75%. 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% by weight.

  The composition of the present technology can also include a detergent. The detergent used herein is a salt of an organic acid (typically a metal salt, but various ammonium salts are known, including quaternary ammonium salts). 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 metal or alkaline earth metal. Suitable metals include sodium, calcium, potassium and magnesium. Typically, the detergent is overbased, which means that there is a stoichiometric excess of metal base above that required to form a neutral metal salt.

  Suitable overbased organic salts include sulfonates that have substantially lipophilic character and are formed from organic materials. Organic sulfonates are well known materials in the lubricant and detergent arts. The sulfonate compound should contain an average of 10 to 40 carbon atoms, such as an average of 12 to 36 carbon atoms or 14 to 32 carbon atoms. Similarly, phenates, salicylates and carboxylates have substantially lipophilic character.

  In the technology of the present invention, the carbon atom may be of aromatic or paraffinic structure, but in certain embodiments, alkylated aromatic compounds are used. A naphthalene-based material can also be used, but the aromatic chosen is the benzene moiety.

  Accordingly, suitable compositions include overbased monosulfonated alkylated benzenes such as monoalkylated benzenes. Alkylbenzene fractions can be obtained from still bottom sources, which are mono-alkylated or di-alkylated. In the present technology, mono-alkylated aromatics are considered superior to dialkylated aromatics in all properties.

  It is desirable to use a mixture of mono-alkylated aromatics (eg, benzene) to obtain the mono-alkylated salts (benzene sulfonate or toluene sulfonate) of the present technique. A mixture in which a substantial portion of the composition contains a polymer of propylene as a source of alkyl groups helps to dissolve the salt. The use of monofunctional (eg, monosulfonated) materials avoids molecular cross-linking and reduces salt precipitation from the lubricant.

  The salt may be “overbased”. Overbasing means that there is a stoichiometric excess of the metal base than is necessary for the anion of the neutral salt. Excess metal due to overbasing has the effect of neutralizing the acid that may be present in the lubricant. Typically, the excess metal will be present in a ratio of up to 30: 1, for example 5: 1 to 18: 1, on an equivalent basis, greater than the amount required to neutralize the anion.

  The amount of overbased salt used in the composition is typically 0.025 to 3 or 5% by weight, eg 0.1 to 1.0% by weight or 0.2% on an oil-free basis. ~ 4% by weight. In other embodiments, the final lubricating composition may be free of detergent, substantially free of detergent, or contain very low amounts of detergent. Thus, for example, for calcium overbased detergents, the amount is less than 250 ppm calcium, such as 0-250, or 1-200, or 10-150, or 20-100 or 30-50 ppm calcium, or the above An amount that provides an amount of calcium less than any of the non-zero amounts. Such small amounts of detergents may be particularly suitable for automatic transmission applications. This contrasts with more traditional automatic transmission formulations that may contain sufficient calcium detergent to provide 300-600 ppm of calcium. Formulations suitable for internal combustion engine lubrication typically have a non-zero amount of detergent, for example, 0.1-5%. Overbased salts are usually made in up to about 50% oil and have a TBN range of 10-800 or 10-600 on an oil-free basis. Borated and non-borated overbased detergents are described in US Pat. Nos. 5,403,501 and 4,792,410.

  The composition of the present technology, in certain embodiments, comprises at least one phosphorus compound, such as an organic or inorganic phosphorus acid (including organic or inorganic phosphorus acids) that may be present in an amount of 0.002 to 1.0% by weight. phosphorous acid), organic or inorganic phosphorus acid salts, organic phosphorus acid esters or derivatives thereof. In certain embodiments, the amount of such phosphorus compound is that amount that provides 0.025-0.085% or 0.02-0.08% phosphorus to the composition. Phosphoric acid, salt, ester or derivative thereof includes phosphoric acid, phosphorous acid, phosphoric acid ester or salt thereof, phosphite, phosphorus-containing amide, phosphorus-containing carboxylic acid or ester, phosphorus-containing ether, and these A mixture is included. Some phosphorus materials may serve as antiwear agents.

  In one embodiment, the phosphorus acid, ester or derivative may be an organic or inorganic phosphorus acid, a phosphorus acid ester, a phosphorus acid salt or a derivative thereof. Phosphorus acids include phosphoric acid, phosphonic acid, phosphinic acid, and thiophosphoric acid including dithiophosphoric acid, as well as monothiophosphoric acid, thiophosphinic acid and thiophosphonic acid. One group of phosphorus compounds is the formula

Wherein R ¹ , R ² , R ³ are alkyl or hydrocarbyl groups, or one of R ¹ and R ² may be H. It is. The material is usually a 1: 1 mixture of dialkyl phosphate and monoalkyl phosphate. Such compounds are described in US Pat. No. 5,354,484.

  85% phosphoric acid is a material suitable for addition to a fully formulated composition, which is 0.01-0.3% by weight, for example 0.03-0. May be included at a level of 2 or ~ 0.1%. Phosphoric acid can form salts with basic components such as succinimide dispersants.

  Other phosphorus-containing materials that may be present include dialkyl phosphites (sometimes referred to as dialkyl hydrogen phosphonates) such as dibutyl phosphite. Still other phosphorus materials include phosphorylated hydroxy substituted triesters of phosphorothioic acid and amine salts thereof, and non-sulfur containing hydroxy substituted di-esters of phosphoric acid, non-sulfur containing phosphorylated hydroxy substituted di- or triesters of phosphoric acid And amine salts thereof. These materials are further described in US Patent Publication No. 2008-0182770.

  Other materials can optionally be included in the composition of the present technology, provided that they are not incompatible with the above required components or specifications. Such materials include antioxidants (ie, oxidation inhibitors), hindered phenolic antioxidants, aromatic secondary amine antioxidants such as dinonyldiphenylamine, and other alkyl substituents (mono Known variants such as monononyl diphenylamine and diphenylamine using-or di-octyl), sulfurized phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, and organic sulfides, disulfides and polysulfides such as , 2-hydroxyalkyl, alkylthioether, or 1-t-dodecylthio-2-propanol or sulfurized 4-carbobutoxycyclohexene or other sulfurized olefins. In some embodiments, the amount of antioxidant can be 0.1-5% by weight or 0.15-2.5% or 0.2-4%.

  Corrosion inhibitors such as tolyltriazole and dimercaptothiadiazole and oil-soluble derivatives of such materials may also be included. Other optional ingredients include seal swelling agents designed to keep the seal soft, such as isodecyl sulfolane or phthalate esters. Pour point depressants such as alkyl naphthalene, polymethacrylate, vinyl acetate / fumarate or / maleate copolymers and styrene / maleate copolymers are also acceptable. Other materials include antiwear agents such as zinc dialkyldithiophosphates, tridecyl adipate, and various long chain derivatives of hydroxycarboxylic acids such as tartrate as described in U.S. Patent Application Publication No. 2006-0183647, Tartaric amide, tartaric imide and citrate. These optional materials are known to those skilled in the art, are generally commercially available, and are described in further detail in published European Patent Application No. 761,805. Known materials such as corrosion inhibitors (eg, tolyltriazole, dimercaptothiadiazole), dyes, fluidizing agents, odor masking agents and antifoaming agents can also be included. Organoborates and borates can also be included.

  The components may be in the form of a fully formulated lubricant or in the form of a concentrate in a smaller amount of lubricating oil. When they are present in the concentrate, their concentration is generally directly proportional to its concentration in a more diluted form in the final blend.

  The compositions described herein can be used in a method of lubricating a mechanical device that includes supplying the mechanical device with any of the lubricant compositions described herein. The mechanical device can be an automatic transmission found in a vehicle such as an automobile. Automatic transmissions include continuously variable transmissions and two-stage clutch transmissions, as well as transmissions for various types of gasoline engines, diesel engines, and hybrid engines (including gasoline / electric hybrids). Mechanical devices include two and four cycle engines, gasoline fuel engines, diesel fuel engines, spark ignition engines, compression ignition engines, sump lubrication engines, and engines that supply lubricant in a mixture with fuel. An internal combustion engine is also included.

  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 rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

Hydrocarbon substituents, ie, aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic-substituted aromatic substituents, aliphatic-substituted aromatic substituents And alicyclic-substituted aromatic substituents, as well as cyclic substituents whose rings are completed through another part of the molecule (eg, two substituents together form a ring);
Substituent hydrocarbon substituents, ie in the context of the present technology, the predominantly hydrocarbon nature of substituents (eg halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso and sulfoxy) Substituents containing non-hydrocarbon groups that do not change;
Hetero substituents, i.e., which have predominantly hydrocarbon character in the context of the present technology, contain other than carbon in the ring or chain, otherwise consist of carbon atoms, pyridyl, furyl, Substituents including substituents such as thienyl and imidazolyl. Heteroatoms include sulfur, oxygen and nitrogen. Generally, there are no more than two or one non-hydrocarbon substituent for every ten carbon atoms in the hydrocarbyl group; typically there are no non-hydrocarbon substituents in the hydrocarbyl group.

  It is known that some of the above materials can interact in the final formulation, and therefore the components of the final formulation can be different from those originally added. For example, metal ions (eg of detergents) can migrate to other acidic or anionic sites of other molecules. The products formed thereby may not be easily described, including products formed using the compositions of the present technology in their intended use. Nevertheless, all such modifications and reaction products are included within the scope of the present technology; the present technology includes compositions prepared by admixing the components described above.

Preparation Example A. Reaction of Duomeen® 2HT with pyromellitic anhydride to obtain pyromellitic acid diimides, for example those of structure (I) above. Duomeen® 2HT is (H Tallow) ₂ N— (CH ₂ ) ₃ NH ₂ , where H Tallow indicates hydrogenated tallow, approximately 64% C18 groups, 31% C16 groups, 4% Is a trade name of Akzo Nobel for a diamine that can be represented by:

  A 2 L round bottom flange flask is equipped with a stirrer, nitrogen inlet, thermocouple, Dean-Stark trap, and condenser. A flask is charged with 56.7 g pyromellitic anhydride and 750 mL xylene. The mixture is heated to about 110 ° C. with stirring, and 300 g Duomeen® 2HT is added dropwise over about 2 hours. The mixture is heated to 145 ° C. and stirred for 4 hours, then further heated to 190 ° C. for 1 hour under vacuum to remove the solvent and any remaining water by distillation and then cooled. Thereby, an amount of 332 g of diimide is obtained.

  Preparation Example B. Reaction of 2-ethylhexanol with pyromellitic anhydride. Add 21.2 g of pyromellitic anhydride and 25.6 g of 2-ethylhexanol to a 250 mL 4-neck flask equipped with a mechanical stirrer, nitrogen inlet, thermocouple, and Dean-Stark trap fitted with a condenser tube on top. To do. The reaction mixture is heated to 150 ° C. over 30 minutes and held at that temperature for 2 hours. Thereafter, an additional 26.2 g of 2-ethylhexanol and 0.24 g of methanesulfonic acid are added in several portions to increase the temperature to 156-160 ° C. and stirred at this temperature for about 2 hours. The reaction mixture is heated to 180 ° C. and stripped under reduced pressure to give the product.

Base formulation I is prepared using the following ingredients:
6. 24% polymer viscosity modifier (including 30% diluted oil)
0.2% polymer pour point depressant (including 50% diluted oil)
5.65% succinimide dispersant (including 44% diluted oil)
1.66% seal swell agent 1.02% amine and sulfur-containing antioxidant 0.30% phosphite and phosphonate friction modifier 0.15% borate ester friction modifier 0.09% phosphoric acid (85%)
0.1% corrosion inhibitor 0.014% commercial antifoam 1.8% diluted oil remaining: mineral fluid.

Base formulation II is prepared using the following ingredients:
9.6% polymer viscosity modifier (including 75% diluted oil)
0.2% polymer pour point depressant (including 50% diluted oil)
3.5% succinimide dispersant (including 44% diluted oil)
0.4% seal swell agent 0.9% amine antioxidant 0.20% phosphite friction modifier 0.10% phosphoric acid (85%)
0.037% Commercially available antifoam, pigment, and other minor constituents remaining: mineral fluid.

  Test lubricants are prepared by adding one of the test materials specified in the table below to the indicated base formulation. The obtained lubricant is subjected to a VSFT test which is a variable speed friction test. The VSFT device consists of a disk that can be a metal or other friction material that rotates relative to the metal surface. The friction materials used in the specific tests are various commercially available friction materials commonly used in automatic transmission clutches as shown in the table. The test is performed at three temperatures and two load levels. The coefficient of friction measured with VSFT is plotted against sliding speed (50 and 200 rpm) over several speed sweeps at constant pressure. Results may be shown as a slope of the μ-v curve as a function of time, determined at 4 hour intervals from 0 to 52 hours, at 40, 80 and 120 ° C. and 24 and 40 kg (235 and 392 N) forces. Report. Typically, the slope is initially positive with some variation and can gradually decline, and will likely become negative after a period of time. It is desirable that the period of positive slope is longer.

  Data is first collected as a table of slope values as a function of time for each trial. Each formulation at each temperature is assigned a “gradient score” for ease of analysis and comparison. At each temperature, the positive slope value of the first 7 hours at 24 kg (0-24 hours) and the slope value of the first 7 measurements at 40 kg (thus a total of 14 slope values) at each temperature ) Is expressed as “A” in%. The percentage of the slope value at two pressures (total of 14 measurements) within the second 24 hours (28-52 hours) being positive is displayed as “B”. The slope score is defined as A + 2B. The additional weight given later in the test is to reflect the greater importance (and difficulty) of preparing a persistent fluid that retains a positive slope later in the test. A maximum score of 300 represents a fluid that consistently exhibits a positive slope throughout the test. A more detailed description of an overview of reporting slope scores and an exemplary calculation of slope scores can be found in US Patent Application Publication No. 2010-021490, August 29, 2010, Vickerman et al .; see paragraphs 0093-0096. I want.

* Reference Example or Comparative Example a. Friction material: labeled Raybestos ™ 4211 or Borg Warner ™ 6100.

  The results show desirable friction performance with the inventive material, especially compared to the base formulation without the inventive material. The results also show that better performance can be obtained at a relatively high concentration of 2.5% compared to 1.0%.

  Further friction tests show further features of the present technique. The fluid of Example 3 containing 2.5% pyromellitic diimide of Preparation A in Base Formula I was subjected to the Ford30K Durability Dynamic Friction Test (Dynax ™ D-0530-31). To serve. Friction between the steel and the friction clutch friction plate is measured during the engagement process. The midpoint value of the dynamic friction coefficient is set to 50 ms interval, 1800 r. p. m. In the middle and repeatedly determined at 4 cycles / min between 400 and 30,000 engagement cycles. The temperature of the lubricant is 135 ° C.

  A plot of the midpoint value of the coefficient of friction is shown in FIG. The solid line at the top indicated by diamonds indicates the coefficient of friction for the fluid of Example 3 containing pyromellitic acid diimide. The lower dashed line indicated by a white circle shows the same baseline fluid without the use of pyromellitic diimide.

  The test results show that the addition of pyromellitic diimide of Preparation A significantly increases the dynamic coefficient of friction imparted by the lubricant to the desired level and this level is maintained through 30,000 cycles. . This is a unique and advantageous performance. Because traditionally, dispersants with long polyisobutylene “tail” components need to provide a high level of dynamic friction, but such dispersants can provide poor performance at low temperatures (excessively high viscosity). Because. The technology of the present invention is capable of formulating a lubricant having a high dynamic coefficient of friction regardless of the absence or use of small amounts of such dispersants.

  The technique of the present invention also provides good anti-sudder durability for wet clutch lubrication typically found in automatic transmissions.

A series of lubricant formulations is prepared containing additional components typically used in heavy duty diesel engine lubricants. The base formulation was 7.6% olefin copolymer viscosity modifier (including 92% diluted oil), 0.15% pour point depressant (diluted with oil), 5.1-100N mineral fluid, 5.1. % Succinimide dispersant (47% diluted oil), 0.63% zinc dialkyldithiophosphoric acid (9% oil), a mixture of 2.2% antioxidant, 1.53% overbased calcium sulfonate detergent ( 42% oil), 0.1% oleamide, and 90 ppm of a commercial antifoam. In the lubricant, the further components shown in the table below (expressed in% by weight) (in certain cases 0.2% tetraester of pyromellitic acid with 2-ethyl-hexanol from Preparation Example B above) Add). The resulting lubricant formulation is subjected to corrosion testing of copper and lead specimens. In this test, 50 cm ³ of air is bubbled into a 50 g lubricant sample containing Cu and Pb specimens, typically at 135 ° C., typically for 216 hours. The test results are also reported in the table below.

* Reference Example or Comparative Example a. Commercially available molybdenum-containing compositions (providing 0.05% Mo for lubricant formulations)
b. ASTM D 130: 1A = clean or slightly cloudy; 4C = heavy black precipitate Glycerol monooleate is known to cause excessive lead corrosion. This excessive corrosion is significantly mitigated by the presence of pyromellitic acid ester. Copper corrosion, as assessed by visual rating, is typically improved by the presence of pyromellitic esters, especially when molybdenum is also present (copper corrosion measured by ppm Cu is not significantly affected).

Example 17. A lubricant composition suitable for use as an engine lubricant is prepared using the following ingredients (wt%).
1.0% tetraester of pyromellitic acid derived from Preparation Example B and 2-ethylhexanol 8% polymer viscosity modifier (including 91% diluted oil)
0.15% polymer pour point depressant (25% oil)
5.1% succinimide dispersant (47% oil)
0.48% zinc dialkyldithiophosphoric acid (9% oil)
1.53% overbased calcium sulfonate (42% oil)
0.1% carboxylic acid ester friction modifier 2% hindered phenol ester antioxidant 1% amine antioxidant oil of lubricating viscosity-100% remaining.

  The lubricant composition of Example 17 exhibits one or more of good antiwear performance and good coefficient of friction.

  Examples 18, 19, and 20. An imide having the structure shown below is prepared.

  The materials of Examples 18, 19, and 20 are added at 2.5% by weight to each of the above two base formulations I and II characteristic of automatic transmission fluids. These are subjected to the VSFT test (above) using BorgWarner ™ 6100 friction material. The results are shown in the table below as “gradient score” (defined above).

  Each of the documents referred to above is incorporated herein by reference. Citation of any document is not an admission that such document is considered a prior art and constitutes general knowledge of those skilled in the art. All quantities in this description that specify the amount of material, reaction conditions, molecular weight, number of carbon atoms, etc., unless otherwise stated or explicitly stated, are qualified with the word “about” Should be understood. Unless otherwise indicated, the chemicals or compositions referred to herein include isomers, by-products, derivatives, and other such materials as would normally be understood to be present in commercial grade products. It should be construed as a commercial grade material that may contain. However, unless otherwise indicated, the amount of each chemical component is shown excluding any solvent or diluent oil that may conventionally be present in the commercial material. It should be understood that the upper and lower amount, range and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the present technology can be used together with ranges or amounts for any of the other elements. As used herein, the expression “consisting essentially of” is intended to include materials that do not substantially affect the basic and novel characteristics of the composition under consideration.

Claims (15)

A composition comprising:
(A) oil of lubricating viscosity, and (b) 0.0001 to 10 weight percent or less:
(I) at least, but is bound to two carbon atoms which are separated by either being attached to two adjacent carbon atoms or one atom not bound to the position of each other meta on the aromatic ring 2 An aromatic polycarboxylic acid having one carboxyl group, or a mixture or reactive equivalent thereof, wherein the aromatic polycarboxylic acid or reactive equivalent thereof is represented by at least one succinic acid group or reactive equivalent thereof. An aromatic polycarboxylic acid or a mixture thereof or a reactive equivalent thereof containing a substituted aromatic ring;
(Ii) A composition comprising a condensation product with an aliphatic primary amine containing 6 to 80 carbon atoms, wherein the condensation product comprises an imide or an amide. The composition according to claim 1, wherein the aliphatic primary amine comprises a primary amine containing 12 to 60 carbon atoms and further containing a secondary or tertiary amino group or an ether group. object. The composition according to claim 1, wherein the condensation product contains a cyclic imide. The aromatic polycarboxylic acid or reactive equivalent thereof comprises an aromatic group having at least two carboxylic acid groups or reactive equivalents thereof on at least two aromatic carbon atoms. The composition according to claim 1. 5. The composition of claim 4, wherein the aromatic polycarboxylic acid or reactive equivalent thereof comprises a benzene ring having at least two carboxylic acid groups or reactive equivalents on adjacent carbon atoms. The aromatic polycarboxylic acid or a reactive equivalent thereof includes a naphthalene structure, which includes a naphthalene structure having two carboxylic acid groups arranged at the 1-position and the 8-position of the naphthalene structure or a reactive equivalent thereof. The composition according to claim 4. The composition according to any one of claims 1 to 5, wherein the condensation product comprises a diimide. The composition of any one of claims 1-3, 4, 5, or 7, wherein the condensation product comprises pyromellitic acid diimide. The aliphatic primary amine has the formula:
_{H 2 N- (C n H 2n} ) -X-R 1
In the formula, n is 2 to 6,
X is O or N—R ² ;
R ¹ is an alkyl group of at least 8 carbon atoms;
R ² is H or an alkyl group;
The composition according to any one of claims 1 to 8, which is represented by: The composition according to any one of claims 1 to 9, wherein the aliphatic primary amine comprises N, N-dialkyl-1,3-propanediamine. The N, N-dialkyl-1,3-propanediamine is N, N-di- (hydrogenated tallow) -1,3-propanediamine, N, N-dicoco-1,3-propanediamine, or N, 11. A composition according to claim 10 comprising N-diisostearyl-1,3-propanediamine. The condensation product is

Wherein each of R ¹ and R ³ is independently an alkyl group of 8 to 22 carbon atoms, and each of R ² and R ⁴ is independently hydrogen or 1 to 22 carbons. An alkyl group of atoms, provided that the total number of carbon atoms in R ¹ and R ² is at least 13 and the total number of carbon atoms in R ³ and R ⁴ is at least 13;
The composition of any one of claims 1-3, 4, 5, or 7-11, comprising a material represented by: ^{R 1, R 2, R 3} , and ^{R 4,} tallow amine, cocoamine or iso alkyl group indicating characteristics of stearylamine The composition of claim 12. The method further comprises at least one additive selected from the group consisting of organic borate esters, organic borates, organic phosphorus esters, organic phosphorus salts, inorganic phosphorus salts, and inorganic phosphorus acids. 13. The composition according to any one of 12. 15. A method of lubricating a mechanical device, comprising providing the device with a composition according to any one of claims 1-14.

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