alkylaminoacetamides and alkyl ether aminoacetamides

Abstract

Alkylaminoacetamides and alkyl ether aminoacetamides, and their use as organic friction modifiers in lubricant formulations, are described. Formulations containing alkylaminoacetamides and alkyl ether acetamides, as well as methods for synthesizing these compounds, are also described.

Description

[0001] Cross-references to other applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 603,301, filed November 28, 2023, which is incorporated herein by reference. Technical Field

[0003] This invention relates to alkylaminoacetamides and alkyletheraminoacetamides, their use as organic friction modifiers in lubricant formulations, formulations containing them, and methods for synthesizing them. Background Technology

[0004] Friction modifiers (FMs) are added to lubricants to reduce friction and wear on machine parts. They are particularly important in boundary lubrication mechanisms, preventing direct contact between solid surfaces and significantly reducing friction and wear. They are especially useful in limited-slip gear oils, automatic transmission fluids, slideway lubricants, and multi-purpose tractor fluids.

[0005] Reducing friction loss through more efficient lubrication is a key objective in improving fuel economy and reducing carbon dioxide emissions. Therefore, friction modifiers are increasingly being incorporated into automotive crankcase lubricants.

[0006] There are several different types of friction modifiers. For example:

[0007] Organic compounds are important additives in modern engine oils and are also used in fuels. They adsorb onto metal surfaces and self-assemble to form an incompressible monolayer that prevents contact between rough surfaces and reduces friction and wear.

[0008] Organic molybdenum compounds were initially developed as wear-resistant additives, but have since been found to be highly effective in reducing boundary friction. They are currently used in many engine oils and more recently in gear oils. They reduce friction by forming a two-dimensional molybdenum disulfide layer on the friction surface.

[0009] Organozinc compounds are a class of coordination compounds developed in the 1940s, characterized by the anionic bonding of zinc with dialkyl dithiophosphate. They function as wear-resistant compounds and are commonly used in engine oils, greases, and lubricants.

[0010] Functionalized polymers can be tailored to specifically adsorb onto polar surfaces and have been shown to significantly reduce friction and wear.

[0011] While the friction modifiers listed above offer numerous advantages, they also present several challenges. The most common type of friction modifier is zinc dithiophosphate (ZnDTP or ZDDP). However, zinc and phosphorus emissions have been reported to potentially damage catalytic converters. Consequently, the use of ZDDP is declining in many applications. Other metal-containing compounds, such as molybdenum dithiocarbamate (MoDTC), can also cause some emission problems.

[0012] Issues related to ZDDP mean that organic ashless friction modifiers are becoming increasingly important. Organic friction modifiers are typically long, straight-chain hydrocarbons consisting of at least 10 carbon atoms and a polar group at one end. The polar group is one of the determinants of a molecular effectiveness as a friction modifier. The most common FMs are esters of fatty acids and polyols, fatty acid amides, fatty acid-derived amines, and organic dithiocarbamates or dithiophosphates. Long-polarity friction modifiers in lubricants are described in EP1367116, EP0799883, EP0747464, US 3,933,659, and EP335701 (the contents of which are incorporated herein by reference). Glyceryl monooleate (GMO) is another example of an organic FM. It is described in US 5,885,942, 5,866,520, 5,114,603, 4,957,651, and 4,683,069, the contents of which are incorporated herein by reference.

[0013] The problem with most organic lubricants is that they contain hydrolyzable groups, such as ester groups, which can be hydrolyzed and degraded. This leads to a loss of friction-modifying properties and the production of hydrophilic decomposition products that are immiscible with oils and lubricants.

[0014] Therefore, there is a need to produce a stable friction modifier that will not damage the catalyst converter. Summary of the Invention

[0015] Therefore, the object of the present invention is to provide compounds with excellent friction-modifying properties that do not produce harmful emissions and are stable. Attached Figure Description

[0016] Figure 1 The graph shows a decrease in the coefficient of friction between Mobil 10W-30 and the FM-A-containing material of Example 5.

[0017] Figure 2 The graph shows a decrease in the coefficient of friction between Mobil 10W-20 and the FM-A-containing material of Example 6. Detailed Implementation

[0018] This invention will be described with reference to specific aspects and embodiments.

[0019] It should be noted that the term "comprising" as used in the claims should not be construed as limiting to the means listed below, and it does not exclude other elements or steps. Therefore, it should be interpreted as specifying the presence of the stated feature, step, or component when mentioned, but does not exclude the presence or addition of one or more other features, steps, components, or a collection thereof. Thus, the scope of the expression "a mixture comprising components X and Y" should not be limited to mixtures consisting solely of components X and Y. For the purposes of this invention, it means that the only relevant components of the mixture are X and Y.

[0020] Throughout this specification, the phrase "in one embodiment" or "implementation" is used. Such a reference indicates that a particular feature described for that embodiment is included in at least one embodiment of the invention. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing in various places throughout this specification do not necessarily refer to the same embodiment, although they may refer to the same embodiment. Furthermore, it will be apparent to those skilled in the art that the specific features or characteristics described can be combined in any suitable manner in one or more embodiments.

[0021] The terms "preferred" and "ideally" refer to embodiments that provide certain benefits in specific circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, describing one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0022] The terms “optional” or “optionally” refer to events or situations described below that may or may not occur, and the description includes both scenarios in which the events or situations occur and scenarios in which they do not occur.

[0023] When substituents are defined by their conventional chemical formula written from left to right, they also include chemically identical substituents that are produced when the structure is written from right to left, for example, -CH2O- is equivalent to -OCH2-.

[0024] It is understood that, in order to provide embodiments according to the invention, although preferred embodiments and / or materials have been discussed, various adjustments or changes may be made without departing from the scope and spirit of the invention.

[0025] In one embodiment, the present invention provides a compound selected from general formulas (I), (II), (III), (IV), (V), and (VI), and mixtures thereof:

[0026] (I)

[0027] (II)

[0028] (III)

[0029] (IV)

[0030] (V)

[0031] (VI)

[0032] Where R is selected from alkyl, cycloalkyl, alkyl ether, aryl ether and aryl;

[0033] R Selected from alkyl, cycloalkyl, and aryl groups; and

[0034] R It is independently selected from H, methyl, ethyl, or combinations thereof.

[0035] Compounds of the above general formulas (I), (II), (III), (IV), (V), and (VI) possess excellent friction-reducing capabilities and can be included in a variety of formulations. Aminoacetamide products contain amine and amide groups at their polar heads, which facilitates strong adsorption of the molecules to surfaces in contact with the friction modifier, particularly metal surfaces. The straight-chain structure of the hydrophobic tails ensures strong van der Waals forces between these tails, promoting the formation of self-assembled monolayers. These unique molecular structures make these molecules excellent friction modifiers for lubricants.

[0036] Furthermore, since the compounds of the present invention do not contain hydrolyzable groups, they exhibit good storage stability and are insensitive to water. The friction modifiers of the present invention do not contain any heavy metal atoms, thus exhibiting favorable emission characteristics.

[0037] The term "storage stability" refers to the ability of a composition to be stored at ambient temperature in a suitable container for a period of time, such as at least three months, at least four months, at least five months, or at least six months, without significant changes in its performance in the application or final application (e.g., slight (less than about 5%, less than about 4%, or less than about 3%) or no crystallization and / or slight (less than about 5%, less than about 4%, or less than about 3%) or no increase in viscosity).

[0038] Friction modifiers are any substances that can reduce the slight surface contacts (slipping and rolling) that may occur in a given machine design. In this document, the term boundary lubricant additive may also be used to refer to friction modifiers.

[0039] The term "alkyl" refers to a straight-chain or branched hydrocarbon group having 1 to 50 carbon atoms, and "substituted alkyl" refers to an alkyl group further having one or more substituents selected from hydroxyl, alkoxy, mercapto, cycloalkyl, heterocyclic, aryl, heteroaryl, aryloxy, halogen, trifluoromethyl, cyano, nitro, nitro ketone, amino, amide, C(O)H, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide, and thioacyl. Examples of alkyl groups include butyl, isobutyl, sec-butyl, tert-butyl, propyl, isopropyl, ethyl, and methyl.

[0040] Aryl groups are functional groups derived from simple aromatic rings, i.e., rings containing delocalized π electrons, such as benzene rings. As used herein, the term aryl can refer to pure hydrocarbon aryl groups and heteroaryl groups (e.g., aryl groups containing heteroatoms selected from N, O, or S).

[0041] In some implementations, R is C 4-100 Straight-chain or branched alkyl groups. For example, -C4H9 or -C 100 H 201 In a preferred embodiment, R is C. 12 -C 22 Straight-chain or branched alkyl groups.

[0042] In some implementations, R is a 5- or 6-membered saturated cycloalkyl group.

[0043] In some implementation schemes, R C 4-100 Straight-chain or branched alkyl groups. For example, -C4H9 or -C 100 H 201 In a preferred embodiment, R C 12 -C 22 Straight-chain or branched alkyl groups.

[0044] In some implementation schemes, R It is a 5- or 6-membered saturated cycloalkyl group.

[0045] In some implementation schemes, R C 4-100 Straight-chain or branched alkyl ethers.

[0046] Another aspect of the present invention is a friction modifier comprising compounds of general formulas (I), (II), (III), (IV), (V), (VI) or combinations thereof.

[0047] In some embodiments, the friction modifier may contain other components selected from lubricants, oils, detergents, dispersants, wear-resistant agents, EP agents, antioxidants, and combinations thereof.

[0048] In another embodiment, the invention includes a composition comprising the above-described friction modifier and optionally one or more additional components selected from lubricants, oils, detergents, dispersants, wear-resistant agents, EP agents, antioxidants, and combinations thereof.

[0049] Organic friction modifiers used in lubricant formulations are also good friction modifiers for fuels. Because the above-mentioned aminoacetamide compounds perform better than commercially available organic friction modifiers in lubricant formulations, the compounds of this invention are also used as friction modifiers in fuels (such as gasoline).

[0050] In one aspect of the invention, a method for adjusting the coefficient of friction between at least two surfaces is provided, the method comprising contacting at least one surface with a composition comprising the friction modifier.

[0051] In one aspect of the invention, the use of the aforementioned friction modifier is provided for adjusting the coefficient of friction between at least two surfaces.

[0052] The coefficient of friction of a composition can be measured using any method known to those skilled in the art. The coefficient of friction is the ratio of the frictional force resisting the motion of two contacting surfaces to the normal force pressing the two surfaces together. It is typically expressed in µ.

[0053] In some implementations, adjusting the coefficient of friction may include reducing the coefficient of friction by at least 60%, at least 50%, at least 40%, at least 20%, at least 10%, or at least 5%.

[0054] Preferably, the compound of the present invention reduces the coefficient of friction between the two surfaces.

[0055] Another aspect of the present invention describes a method for preparing a friction modifier, the method comprising reacting a haloacetamide with a compound selected from compounds A, B, and C to prepare compounds of general formulas (I), (II), (III), (IV), (V), and (VI):

[0056] Compound A

[0057] Compound B

[0058] Compound C

[0059] (I)

[0060] (II)

[0061] (III)

[0062] (IV)

[0063] (V) and

[0064] (VI)

[0065] Among them, R, R and R As described above; and

[0066] Where n is 5-100, preferably 12-22.

[0067] In some embodiments, the haloacetamide is chloroacetamide. Chloroacetamide is commercially available.

[0068] In some embodiments, the reaction is carried out under alkaline conditions. Suitable bases include, but are not limited to, organic bases such as pyridine, alkylamines such as methylamine, imidazole, benzimidazole, histidine, guanidine, phosphazene bases, hydroxides of quaternary ammonium cations or some other organic cations, and inorganic bases such as metal hydroxides (e.g., LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2).

[0069] In some embodiments, the reaction is carried out at a temperature of 0-200°C, preferably 50-150°C.

[0070] In some embodiments, the reaction involves reacting compound A and a haloacetate in a 2:1 molar ratio to produce a compound of general formula (I).

[0071] In some embodiments, the reaction involves reacting compound A and a haloacetate in a 1:1 molar ratio to produce a compound of general formula (II).

[0072] In some embodiments, the reaction involves reacting compound B and a haloacetate in a 1:1 molar ratio to produce a compound of general formula (III).

[0073] In some embodiments, the reaction involves reacting compound B with a haloacetate in a 2:1 molar ratio to produce a compound of general formula (IV).

[0074] In some embodiments, the reaction involves reacting compound C and a haloacetate in a 1:1 molar ratio to produce a compound of general formula (V).

[0075] In some embodiments, the reaction involves reacting compound C and a haloacetate in a 2:1 molar ratio to produce a compound of general formula (VI).

[0076] The specific and preferred features of the present invention described above can be appropriately combined with other features.

[0077] The above and other features, characteristics and advantages of the present invention will become apparent from the following detailed description of embodiments in conjunction with the embodiments which illustrate the principles of the invention.

[0078] Example

[0079] The detailed description of this invention can be illustrated by the following examples. All chemicals were supplied by Huntsman International LLC, except for the following:

[0080] 2-Chloroacetamide: Sigma Aldrich

[0081] NaOH solution: Sigma Aldrich

[0082] Toluene: Sigma Aldrich

[0083] TOMAMINE PA-19: Evonik (structure as follows)

[0084]

[0085] Adogen 172: Evonik (structure as follows)

[0086]

[0087] Jeffamine C-300 is supplied by Huntsman and has the following structure

[0088]

[0089] Unless otherwise stated, all parts and percentages in the following examples and throughout the specification are parts by weight or weight percentages. The term "ambient temperature" refers to the temperature of the surrounding working environment (e.g., the temperature of the area, building, or room where the composition is used). The ambient temperature can be about 10-30°C, more specifically 15-25°C.

[0090] Example 1 - Synthesis of Alkyl Polyether Amino Monoacetamide

[0091] 169.1 g (0.5 mol) Jeffamine C-300, 169.1 g toluene, and 46.75 g (0.5 mol) 2-chloroacetamide were placed in a 1000 ml three-necked flask. The mixture was heated to 100 °C while stirring.

[0092] Add 42 g of 50% NaOH solution to the flask, while maintaining the temperature at 100 ± 5 °C. Keep the reaction solution at 100 °C for 1 hour. Cool the reaction to ambient temperature and wash the reaction product twice with deionized water. Remove toluene and water from the organic layer under vacuum (20 torr) and elevated temperature (90 °C).

[0093] The final product is primarily alkyl polyether amino monoacetamide. This product is named Friction Modifier A (FM-A).

[0094] Example 2 - Synthesis of alkyl polyether aminodiacetamide

[0095] 169.1 g (0.5 mol) Jeffamine C-300, 169.1 g toluene, and 93.5 g (1.0 mol) 2-chloroacetamide were placed into a 1000 ml three-necked flask. The flask was stirred and the temperature was raised to 100 °C.

[0096] Add 42 g of 50% NaOH solution dropwise to the flask while maintaining the temperature at 100 ± 5 °C. After 1 hour, cool the reaction flask to ambient temperature. Wash the reaction product twice with deionized water. Remove the organic layer under vacuum and elevated temperature (20 torr and 90 °C) and separate the final product.

[0097] LC-MS analysis showed that the final product was 90% alkyl polyether aminodiacetamide. This product was named Friction Modifier B (FM-B).

[0098] Example 3 - Synthesis of alkyl ether amino monoacetamide

[0099] 143.5 g (0.5 mol) TOMAMINE PA-19, 169.1 g toluene, and 46.75 g (0.5 mol) 2-chloroacetamide were placed in a 1000 ml three-necked flask. The reaction temperature was raised to 100 °C with stirring.

[0100] 42 g of 50% NaOH solution was added dropwise to the flask, and the temperature was maintained at 100 ± 5 °C. After 1 hour, the reaction vessel was cooled to ambient temperature. The resulting product mixture was washed twice with deionized water. The product in the organic layer was removed under vacuum and elevated temperature (20 torr and 90 °C), and the remaining toluene and water were removed.

[0101] The final product is primarily alkyl ether amino monoacetamide. This product is named Friction Modifier C (FM-C).

[0102] Example 4 - Synthesis of Alkylamino Monoacetamide

[0103] 142.5 g (0.5 mol) ADOGEN 172, 169.1 g toluene, and 46.75 g (0.5 mol) 2-chloroacetamide were placed into a 1000 ml three-necked flask. The mixture was stirred while the temperature of the container was raised to 100°C.

[0104] Add 42 g of 50% NaOH solution dropwise to the flask and maintain the temperature at 100 ± 5 °C. After 1 hour of reaction, cool the reaction mixture to ambient temperature. Wash the product mixture twice with deionized water. Separate the product by removing toluene and water from the organic layer under vacuum and elevated temperature (20 torr and 90 °C).

[0105] The final product is primarily alkylamino monoacetamide. This product is named Friction Modifier D (FM-D).

[0106] Example 5 - Evaluation of friction modifiers in Mobil 5W-30 oil

[0107] The friction modifiers prepared in Examples 1-4 were added to Mobil 5W-30 commercially available oil. The coefficient of friction of the commercially available oil containing 0.5% organic friction modifier was determined using a miniature traction machine with a ¾-inch ball on a smooth disk at 100°C and 130°C. The applied load was 36 N (1 GPa contact pressure), and the rotational speed was 0.01–2 m / s. The results are shown in Table 1 below:

[0108] Table 1: Results of Friction Modifier Addition Treatment in Mobil 1 5W-30 Oil at 130°C

[0109]

[0110] These data indicate that the aminoacetamide products (FM-A, B, C, and D) in all embodiments can significantly reduce the coefficient of friction of Mobil 1 5W-30 oil.

[0111] Figure 1 This indicates the total measurement range of FM-A.

[0112] Example 6 - Evaluation of Friction Modifiers in Mobil 1 0W-20 Oil

[0113] The coefficient of friction of Mobil 1 OW-20 oil was measured using the same method as in Example 5 above. The results are shown in Table 2 below.

[0114] Table 2: Results of Friction Modifier Addition Treatment in Mobil 1 0W-20 Oil at 130°C

[0115]

[0116] The data in Table 2 show that the aminoacetamide products (FM-A, B, C and D) in all examples can significantly reduce the coefficient of friction of Mobil 1 0W-20 oil.

[0117] The total range of FM-A is as follows Figure 2 As shown.

Claims

1. A compound selected from general formulas (I), (II), (III), (IV), (V), and (VI): (I) (I) (III) (IV) (V) and (VI) R is selected from alkyl, cycloalkyl, alkyl ether and aryl; R selected from alkyl, cycloalkyl and aryl; and R independently selected from H, methyl, ethyl, or combinations thereof.

2. The compound of claim 1, wherein R is C 4-100 straight-chain or branched alkyl, preferably R is C 12 -C 22 straight-chain or branched alkyl.

3. The compound of claim 1, wherein R is a 5- or 6-membered saturated cycloalkyl group.

4. The compound of claim 1, wherein R is C 4-100 linear or branched alkyl or aryl ethers.

5. The compound of any of the preceding claims, wherein R is C 4-100 straight-chain or branched alkyl, preferably wherein R is C 12 -C 22 straight-chain or branched alkyl.

6. The compound of any one of claims 1-4, wherein R is a 5- or 6-membered saturated cycloalkyl.

7. The compound of any one of claims 1-4, wherein R is C 4-100 a straight-chain or branched alkyl ether or aryl ether.

8. A friction modifier comprising a compound selected from general formulas (I), (II), (III), (IV), (V), (VI) or combinations thereof as defined in any one of claims 1-7.

9. A composition comprising a compound selected from general formulas (I), (II), (III), (IV), (V), (VI) or combinations thereof as defined in any one of claims 1-7, and optionally one or more additional components selected from lubricants, oils, detergents, dispersants, wear-resistant agents, EP agents, and antioxidants.

10. A method for adjusting the coefficient of friction between at least two surfaces, the method comprising contacting at least one surface with the composition of claim 9, the friction modifier of claim 8, or the compound of any one of claims 1-7.

11. A method for preparing a friction modifier, the method comprising reacting a haloacetamide with a compound selected from compounds A, B, and C to prepare a compound of general formula (I), (II), (III), (IV), (V), and (VI) according to any one of claims 1-7: Compound A Compound B Compound C.

12. The method of claim 11, wherein the haloacetamide is chloroacetamide.

13. The method of claim 11 or 12, wherein the reaction is carried out at a temperature of 0-200°C, preferably 50-150°C.

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